EP4316838A1 - Method for producing film laminate - Google Patents
Method for producing film laminate Download PDFInfo
- Publication number
- EP4316838A1 EP4316838A1 EP22780553.8A EP22780553A EP4316838A1 EP 4316838 A1 EP4316838 A1 EP 4316838A1 EP 22780553 A EP22780553 A EP 22780553A EP 4316838 A1 EP4316838 A1 EP 4316838A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adhesive
- ink
- energy ray
- active energy
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 239000000853 adhesive Substances 0.000 claims abstract description 192
- 230000001070 adhesive effect Effects 0.000 claims abstract description 192
- 239000000758 substrate Substances 0.000 claims abstract description 119
- 238000007639 printing Methods 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000003475 lamination Methods 0.000 claims abstract description 26
- 239000002985 plastic film Substances 0.000 claims abstract description 16
- 229920006255 plastic film Polymers 0.000 claims abstract description 16
- 238000010030 laminating Methods 0.000 claims abstract description 10
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 101
- 229920005989 resin Polymers 0.000 claims description 101
- 150000001875 compounds Chemical class 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 36
- 238000010894 electron beam technology Methods 0.000 claims description 32
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000976 ink Substances 0.000 description 178
- 239000000178 monomer Substances 0.000 description 38
- 239000000203 mixture Substances 0.000 description 21
- 239000000049 pigment Substances 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 150000003077 polyols Chemical class 0.000 description 15
- -1 polyethylene Polymers 0.000 description 14
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 238000007645 offset printing Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- 239000004606 Fillers/Extenders Substances 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000005025 cast polypropylene Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012943 hotmelt Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005792 styrene-acrylic resin Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 150000002689 maleic acids Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/14—Printing or colouring
- B32B38/145—Printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
- C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4023—Coloured on the layer surface, e.g. ink
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/02—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/12—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0875—Treatment by energy or chemical effects by wave energy or particle radiation using particle radiation
- B32B2310/0887—Treatment by energy or chemical effects by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
- B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
- B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
Definitions
- the present invention relates to a method for producing a laminated film, the method including: a printing step of applying an active energy ray-curable printing ink to a first substrate film formed of at least a plastic film; an adhesive application step of applying an adhesive; and a lamination step of laminating a second substrate, the steps being performed in this order in-line.
- Lithographic printing is a printing system widely used as a system capable of inexpensively supplying a large volume of printed material at high speed.
- the lithographic system has been mainly applied to printing on paper, but in recent years, application to soft packaging printing for printing on a thin plastic film has been studied mainly for packaging applications such as daily goods, foodstuffs, and pharmaceuticals.
- active energy ray-curable lithographic inks that are instantaneously cured by irradiation with an active energy ray such as a mercury lamp, a metal halide lamp, a light emitting diode, or an electron beam are widely known in many fields from the viewpoints of equipment, safety, environment, and productivity.
- an active energy ray-curable lithographic ink is considered to be a material suitable for printing on a plastic film having poor heat resistance because it can be cured at room temperature in a short time.
- curing of the ink is insufficient in some cases.
- a lithographic ink having both highly sensitive active energy ray curability and water washability and excellent scumming resistance during printing and water resistance of a cured film
- a lithographic ink containing (a) a pigment and (b) a resin having an ethylenically unsaturated group and a hydrophilic group
- another plastic film, a metal foil, a hot-melt film (sealant) or the like is generally bonded to the obtained printed material from the viewpoint of protecting contents, improving impact resistance, imparting heat sealability and the like.
- a method for producing a packaging material using a thin plastic film as a substrate there have been proposed a method including printing a pattern on a substrate, curing an ink by energy ray irradiation, and laminating a heat seal layer on the substrate with an adhesive interposed therebetween (see, for example, Patent Document 2), a method including a step of applying an ink composition to a transparent substrate 1, and drying and curing the ink composition to obtain an ink layer, a step of applying a specific adhesive composition onto the ink layer to form a precursor of an adhesive layer, a step of stacking a substrate 2 onto the precursor of the adhesive layer, and a step of curing the precursor of the adhesive layer to form the adhesive layer (see, for example, Patent Document 3), and the like.
- Patent Documents 2 to 3 disclose a method of laminating a second substrate to a cured ink layer by using an isocyanate-curing adhesive in off-line.
- an active energy ray-curable printing ink is preferably used from the viewpoint of reducing an organic solvent, but there is a problem that the curability of the ink and adhesion between the ink and the plastic film is insufficient.
- a long aging process such as processing at 40°C for 3 days is required for curing the isocyanate-curing adhesive, and there is a problem in productivity.
- an object of the present invention is to solve the problems of the prior art, and to provide a method for producing a laminated film, in which a laminated film excellent in curability of the ink and adhesion between the ink and the second substrate can be produced with high productivity.
- the present inventors have paid attention to the fact that when the surface of the ink is exposed to oxygen in the process of curing the ink by an active energy ray, the curability of the ink and adhesion between the ink and the plastic film become insufficient, and have arrived at the present invention.
- the present invention is a method for producing a laminated film, the method including: a printing step of applying an active energy ray-curable printing ink to a first substrate film formed of at least a plastic film; an adhesive application step of applying an adhesive; and a lamination step of laminating a second substrate, the steps being performed in this order in-line, the method further including a curing step of irradiating the active energy ray-curable printing ink with an active energy ray to cure the active energy ray-curable printing ink after at least the adhesive application step.
- a laminated film excellent in curability of the ink and adhesion between the ink and the second substrate can be produced with high productivity.
- a method for producing a laminated film of the present invention includes a printing step of applying an active energy ray-curable printing ink (hereinafter, may be simply referred to as "ink") to a first substrate film formed of at least a plastic film, an adhesive application step of applying an adhesive, and a lamination step of laminating a second substrate, the steps being performed in this order in-line, the method further including a curing step of irradiating the active energy ray-curable printing ink with an active energy ray after at least the adhesive application step.
- the laminated film in the present invention has at least a cured product of the ink, a cured product of the adhesive, and the second substrate film on the first substrate film. The cured product of the ink only needs to be provided at a necessary position according to the pattern, and does not need to be provided on the entire surface of the laminated film.
- a first aspect of the method for producing a laminated film of the present invention employs an active energy ray-curable adhesive as an adhesive in the adhesive application step, and includes the printing step, adhesive application step, lamination step, and curing step described above in this order. That is, the first aspect of the method for producing a laminated film of the present invention is a method including applying an ink and an adhesive, laminating a second substrate thereon, and then curing the ink and the adhesive by an active energy ray.
- a second aspect of the method for producing a laminated film of the present invention employs a non-solvent isocyanate adhesive as an adhesive in the adhesive application step, and includes the printing step, adhesive application step, curing step, and lamination step described above in this order. That is, the second aspect of the method for producing a laminated film of the present invention is a method including applying an adhesive onto an ink, curing the ink by an active energy ray, and then laminating a second substrate thereon. In both aspects, by continuously performing the printing step to the lamination step or the curing step in a series of production processes, that is, in-line, the lead time is reduced, thus making it possible to improve the productivity.
- the processing loss generated in the lamination step can be reduced as compared with the off-line production in which the printing step and the lamination step are discontinuously performed.
- the presence of the adhesive and/or the second substrate on the surface of the ink suppresses insufficient curing of the ink due to exposure of the surface of the ink to oxygen. This makes it possible to improve the adhesion between the second substrate and the ink, and the curability of the ink.
- Fig. 1 shows a schematic view of an example of the first aspect of the method for producing a laminated film of the present invention.
- An ink is applied to a first substrate film 1 by an offset printing unit 2 of a center drum lithographic printing press (printing step).
- an active energy ray-curable adhesive is applied by a flexographic printing unit 3 of the center drum lithographic printing press (adhesive application step), and a second substrate 5 is laminated thereon using a nip roll 4 (lamination step).
- the ink and the active energy ray-curable adhesive are simultaneously cured by irradiation with an active energy ray by an electron beam irradiation device 6 (curing step).
- Fig. 2 shows a schematic view of an example of the second aspect of the method for producing a laminated film of the present invention.
- An ink is applied to a first substrate film 1 by an offset printing unit 2 of a center drum lithographic printing press (printing step).
- a non-solvent isocyanate-curing adhesive is applied by a flexographic printing unit 3 of the center drum lithographic printing press (adhesive application step), the ink is irradiated with an active energy ray by an electron beam irradiation device 6 via the non-solvent isocyanate-curing adhesive (curing step) to cure the ink, and then a second substrate 5 is laminated thereon using a nip roll 4 (lamination step).
- the first substrate film is formed of a plastic film, and imparts the strength to the laminated film to withstand tension and the like generated in the printing step.
- the plastic film include an oriented polyester film, an oriented polyamide film, an oriented polypropylene (OPP) film, a cast polypropylene film (CPP), and a polyethylene film.
- OPP oriented polypropylene
- CPP cast polypropylene
- the plastic film can be appropriately selected among them according to the required properties such as the leveling property of the ink, appearance quality, barrier property for protecting the contents, and the like, and two or more of these may be used.
- These plastic films may have an easily adhesive layer, an anchor layer, a metal vapor deposition layer, a metal oxide layer, and the like.
- the thickness of the first substrate film is preferably 50 um or less, and more preferably 30 um or less from the viewpoint of processability and cost.
- Examples of the second substrate include an oriented film, a metal film, and a hot-melt film (sealant film). Two or more of these may be used.
- the strength of the laminated film can be improved, thus making it possible to improve the effect of protecting the contents in packaging applications.
- the oriented film include an oriented polyamide film, an oriented polyester film, and an oriented polyolefin film.
- the oriented film may have a metal vapor deposition layer, a metal oxide layer, and the like. In packaging applications, the oriented film can suppress deterioration of the contents due to transmission of oxygen, water vapor, light, and the like to the inside.
- the metal film By using a metal film as the second substrate, it is possible to further suppress deterioration of the contents due to transmission of oxygen, water vapor, light, and the like to the inside.
- the metal film can suppress infiltration of the contents to the outer layer side thereof and suppress deterioration of the outer layer portion.
- the metal film include an aluminum foil.
- a pouch By using a hot-melt film as the second substrate, a pouch can be formed by thermally melting (heat-sealing) the laminated portion of the first substrate and the second substrate.
- the hot-melt film include a cast polypropylene film (CPP), a linear low density polyethylene film (LLDPE), and a low density polyethylene film (LDPE).
- the thickness of the second substrate is preferably 50 um or less, and more preferably 30 um or less from the viewpoint of processability and cost.
- the thickness is preferably 20 um or less, and more preferably 12 um or less.
- the thickness is preferably 20 to 120 ⁇ m.
- the active energy ray-curable printing ink in the present invention refers to one containing a component having an ethylenically unsaturated double bond.
- the active energy ray-curable printing ink in the present invention preferably contains a resin and a compound having an ethylenically unsaturated double bond.
- the active energy ray-curable printing ink contains the resin, fluidity suitable for the ink can be imparted to the active energy ray-curable printing ink, and scattering (misting) of the ink at the time of printing can be suppressed. Note that even a resin having an ethylenically unsaturated double bond is classified as the resin.
- Examples of the compound having an ethylenically unsaturated double bond include monomers and oligomers having an ethylenically unsaturated double bond.
- the molecular weight of the monomer is preferably less than 1,500.
- the oligomer refers to a polymer having a relatively low molecular weight, and the weight average molecular weight thereof is preferably 1,500 or more and 15,000 or less.
- the active energy ray-curable printing ink preferably contain a urethane (meth)acrylate as the oligomer having an ethylenically unsaturated double bond.
- (meth)acrylate is a generic term including acrylate and methacrylate.
- the active energy ray-curable printing ink contains urethane (meth)acrylate
- the cohesive force of the ink can be improved by hydrogen bond interaction derived from a urethane bond. Therefore, it is possible to reduce the difference in viscosity between the ink and the adhesive and to suppress back trapping.
- inclusion of urethane (meth)acrylate improves the affinity of the active energy ray-curable printing ink with the non-solvent isocyanate-curing adhesive, thus making it possible to further improve the adhesion between the ink and the second substrate.
- the active energy ray-curable printing ink may further contain another monomer having an ethylenically unsaturated double bond, a pigment, an acylphosphine oxide compound, or the like.
- Examples of the ink include the printing ink disclosed in International Publication No. 2020/235557 .
- the resin contained in the ink examples include an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, a rosin-modified maleic acid resin, a rosin-modified acrylic resin, an epoxy resin, a polyester resin, a polyurethane resin, and a phenol resin. Two or more of these may be used. Among them, an acrylic resin, a styrene acrylic resin, and a styrene maleic acid resin are preferably used from the viewpoint of ease of synthesis, compatibility with other components, dispersibility of the pigment, and the like.
- the resin contained in the ink preferably has an ethylenically unsaturated double bond and a hydrophilic group.
- a crosslinked structure is formed by a reaction with a radical species in the curing step, so that the sensitivity of the ink to an active energy ray can be improved.
- a strong covalent bond is formed by a reaction with the acryloyl group of urethane (meth)acrylate, so that adhesion of the ink to the first substrate film and resistance of the laminated film to hot water treatment or the like can be improved.
- a strong covalent bond is formed by a reaction with the acryloyl group contained in the active energy ray-curable adhesive, so that adhesion of the ink to the second substrate can be further improved.
- the resin has a hydrophilic group and the active energy ray-curable printing ink contains urethane (meth)acrylate
- the cohesive force of the ink is increased by strong interaction with a urethane bond.
- the resistance of the laminated film to hot water treatment or the like and the scumming resistance of the ink can be improved, thus making it possible to suppress back trapping.
- the term “scumming resistance” means that a phenomenon (scumming) in which the ink is deposited on the printing plate and transferred to the first substrate film hardly occurs in a non-image area to which the ink is not intended to be transferred.
- the term “back trapping” refers to a phenomenon in which the viscosity of the adhesive becomes larger than that of the ink, and the ink is transferred to the adhesive side.
- hydrophilic group examples include a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfo group, and a phosphate group. Two or more of these may be contained.
- the active energy ray-curable printing ink contains urethane (meth)acrylate, among these, a carboxyl group and a hydroxyl group which have good interaction with a urethane bond are preferable, and more preferably, the resin has a carboxyl group and a hydroxyl group.
- the acid value of the resin having an ethylenically unsaturated group, a carboxyl group, and a hydroxyl group is preferably 75 mgKOH/g or more, and preferably 150 mgKOH/g or less.
- the acid value of the resin may be measured according to the neutralization titration in Section 3.1 of the test method of JIS K 0070: 1992.
- the iodine value of the resin having an ethylenically unsaturated group, a carboxyl group, and a hydroxyl group is preferably 1.5 mol/kg or more, and preferably 2.5 mol/kg or less.
- the iodine value of the resin may be measured according to the method described in Section 6.0 of the test method of JIS K 0070: 1992.
- the resin having an ethylenically unsaturated group, a carboxyl group, and a hydroxyl group can be obtained, for example, by copolymerizing a monomer having a carboxyl group, a monomer having a hydroxyl group, and other monomers as necessary, and then adding an ethylenically unsaturated compound having a glycidyl group to the resulting copolymer.
- the weight average molecular weight of the resin is preferably 20,000 or more from the viewpoint of improving the resistance of the laminated film to hot water treatment or the like and the scumming resistance of the ink, and increasing the viscosity of the ink to suppress back trapping.
- the weight average molecular weight of the resin is preferably 50,000 or less from the viewpoint of improving the fluidity of the ink.
- the weight average molecular weight of the resin refers to a value in terms of polystyrene calculated using gel permeation chromatography (GPC).
- the content of the resin in the ink is preferably 5 mass% or more, and more preferably 10.0 mass% or more from the viewpoint of easily adjusting the viscosity ⁇ described later to a preferable range described later.
- the content of the resin in the ink is preferably 40 mass% or less, and more preferably 15 mass% or less from the viewpoint of easily adjusting the viscosity ⁇ described later to a preferable range described later.
- the urethane (meth)acrylate can be obtained by a reaction of a polyol, an isocyanate, and a (meth)acrylate. More specifically, the urethane (meth)acrylate can be obtained, for example, by a method of adding a polyol to an addition reaction product of an isocyanate and a (meth)acrylate.
- the polyol include polyether polyol, polyester polyol, and polycarbonate polyol.
- the isocyanate is preferably, for example, alicyclic isophorone diisocyanate (IPDI) and hydrogenated xylylene diisocyanate from the viewpoint of heat resistance and safety.
- the isocyanate is preferably tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and xylylene diisocyanate (XDI) from the viewpoint of cost, except for applications in which there is a risk of elution into contents such as food to be heat-sterilized.
- the (meth)acrylate is preferably 2-hydroxyethyl acrylate.
- the flexibility and shape conformity of the urethane (meth)acrylate are improved as the molecular weight of the polyol is larger, so that adhesion of the ink to the second substrate can be further improved.
- the molecular weight of the polyol is small and the ratio of the (meth)acrylate is high.
- the weight average molecular weight of the urethane (meth)acrylate is preferably 500 or more from the viewpoint of improving the sensitivity to an active energy ray and further improving the curability.
- the weight average molecular weight of the urethane (meth)acrylate is preferably 10,000 or less from the viewpoint of improving the scumming resistance and the transferability of the ink.
- the urethane (meth)acrylate preferably has two or more (meth)acrylates in one molecule, and more preferably two (meth)acrylates from the viewpoint of compatibility with other ink components and easily adjusting the viscosity ⁇ described later to a preferable range described later.
- the monomer having an ethylenically unsaturated double bond is preferably a (meth)acrylate having a hydroxyl group.
- a (meth)acrylate can improve the resistance of the laminated film to hot water treatment or the like by interaction with the hydrophilic group in the resin.
- Preferred examples of the (meth)acrylate having a hydroxyl group include pentaerythritol tri(meth)acrylate, diglycerin tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate.
- the content of the compound having an ethylenically unsaturated double bond in the ink is preferably 50 mass% or more, and more preferably 65 mass% or more from the viewpoint of easily adjusting the viscosity ⁇ described later to a preferable range described later.
- the content of the compound having an ethylenically unsaturated double bond in the ink is preferably 80 mass% or less from the viewpoint of easily adjusting the viscosity ⁇ described later to a preferable range described later.
- the content of the urethane (meth)acrylate is preferably 1 mass% or more in order to improve adhesion of the ink to the substrate, and is preferably 20 mass% or less from the viewpoint of compatibility with other ink components and easily adjusting the viscosity ⁇ described later to a preferable range described later.
- the pigment examples include an inorganic pigment and an organic pigment.
- the content of the pigment in the ink is preferably 15 mass% or more, and preferably 40 mass% or less in the case of a pigment having a specific gravity of 2 or less.
- the content of the pigment is preferably 40 mass% or more, and preferably 50 mass% or less in the case of a pigment having a specific gravity of more than 2.
- the acylphosphine oxide compound absorbs light in a long wavelength range of 350 nm or more, the acylphosphine oxide compound has high sensitivity even when the ink contains a pigment that absorbs or reflects ultraviolet light.
- the acylphosphine oxide compound has a photobleaching effect in which light absorption is lost after the reaction, and thus exhibits excellent internal curability.
- the acylphosphine oxide compound can improve the compatibility by being combined with a (meth)acrylate having a hydroxyl group, and improve the sensitivity of the ink to the active energy ray.
- acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide.
- the content of the acylphosphine oxide compound in the ink is preferably 5 mass% or more from the viewpoint of improving the sensitivity.
- the content of the acylphosphine oxide compound is preferably 10 mass% or less from the viewpoint of improving storage stability.
- the viscosity ⁇ of the ink at a temperature of 30°C and a shear rate of 300s -1 is preferably 10 Pa ⁇ s or more and 40 Pa ⁇ s or less.
- the conditions of the temperature and the shear rate are assumed to be the temperature at the time of printing and the shear rate when the ink is transferred to the first substrate film.
- the viscosity ⁇ is more preferably 15 Pa ⁇ s or more, and still more preferably 20 Pa ⁇ s or more.
- the viscosity ⁇ is more preferably 35 Pa ⁇ s or less, and still more preferably 30 Pa ⁇ s or less.
- the viscosity ⁇ of the ink in the present invention can be measured using a dynamic viscoelasticity measuring device (rheometer) and a cone plate jig.
- the ink is placed between a cone plate and a lower plate, and the viscosity of the ink is measured from the torque applied to the cone plate when the cone plate rotates.
- the cone plate has a diameter of 40 mm and an inclination angle of 1°, and the gap between the cone plate and the lower plate is 81 um.
- the dynamic viscoelasticity measuring device is heated to 30°C in advance, the ink is placed on the lower plate, and the cone plate jig is set at the measurement position and then allowed to stand at 30°C for 3 minutes.
- the viscosity of the ink is measured while the shear rate is continuously changed logarithmically in the range of the shear rate of 1 to 490s -1 to obtain an approximate expression of the shear rate and the viscosity.
- the viscosity ⁇ at a shear rate of 300s -1 is determined from the approximate expression.
- the viscosity ⁇ of the ink can be adjusted to fall within the above-described range by, for example, using the above-described preferable resin, setting the contents of the resin and the compound having an ethylenically unsaturated double bond to the above-described preferable ranges, and using urethane (meth)acrylate as the compound having an ethylenically unsaturated double bond.
- an active energy ray-curable adhesive or a non-solvent isocyanate-curing adhesive is preferable. These adhesives are excellent in productivity because they do not generally contain an organic solvent to such an extent that the drying step is required and thus the drying step is unnecessary.
- non-solvent means that the content of the organic solvent is 5 mass% or less. The content of the organic solvent is preferably 3 mass% or less.
- the active energy ray-curable adhesive preferably contains a resin and a compound having an ethylenically unsaturated double bond.
- the adhesive can be applied to the uncured ink with good appearance.
- the flexibility of the cured film of the active energy ray-curable adhesive can be moderately improved.
- the active energy ray-curable adhesive contains a compound having an ethylenically unsaturated double bond
- the viscosity of the active energy ray-curable adhesive can be easily adjusted to a range suitable for processing, thus making it possible to improve the appearance of the laminated film.
- the adhesive can be cured by an active energy ray. Note that even a resin having an ethylenically unsaturated double bond is classified as the resin.
- the resin preferably contains an isocyanate-curing resin.
- the isocyanate-curing resin contains a polyol compound and a polyisocyanate compound.
- the flexibility of the cured film of the adhesive can be moderately improved.
- the adhesion strength as a laminate can be further improved when a laminate obtained by applying the adhesive to the first substrate and laminating the second substrate is aged.
- the active energy ray-curable adhesive may further contain a leveling agent, an extender pigment, and the like as necessary.
- Examples of the resin in the active energy ray-curable adhesive include those exemplified as the resin as a raw material of the ink. Among them, an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, and a polyurethane resin are preferably used from the viewpoint of adhesion to the ink, film strength after curing, and the like.
- the resin in the active energy ray-curable adhesive preferably has an ethylenic double bond group, and inclusion of the resin having an ethylenic double bond group can further improve the strength of the cured film of the adhesive.
- the weight average molecular weight of the resin in the active energy ray-curable adhesive is preferably 20,000 or more and 50,000 or less.
- the weight average molecular weight of the resin refers to a value in terms of polystyrene calculated using gel permeation chromatography (GPC).
- the content of the resin in the active energy ray-curable adhesive is preferably 10 mass% or more from the viewpoint of suppressing repelling of the adhesive at the time of application and further improving the flexibility of the cured film.
- the content of the resin in the active energy ray-curable adhesive is preferably 40 mass% or less from the viewpoint of suppressing back trapping by appropriately lowering the viscosity of the adhesive with respect to the ink and easily adjusting the viscosity ( ⁇ 1) described later to a preferable range described later.
- the compound having an ethylenically unsaturated double bond a monomer having an ethylenically unsaturated double bond is preferable.
- the compound having an ethylenically unsaturated double bond preferably have two or more ethylenically unsaturated double bonds in one molecule because it has high curability.
- the compound having an ethylenically unsaturated double bond preferably has six or less ethylenically unsaturated double bonds in one molecule from the viewpoint of improving the flexibility of the cured film of the adhesive.
- pentaerythritol tri(meth)acrylate diglycerin tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, and ethoxylated trimethylolpropane tri(meth)acrylate are preferable.
- the content of the compound having an ethylenically unsaturated double bond in the active energy ray-curable adhesive is preferably 60 mass% or more from the viewpoint of improving the strength of the cured film of the adhesive and easily adjusting the viscosity ⁇ 1 described later to a preferable range described later, and is preferably 90 mass% or less from the viewpoint of improving the flexibility of the cured film of the adhesive.
- the active energy ray-curable adhesive is preferably a non-solvent adhesive, that is, the content of the organic solvent is preferably 5 mass% or less, and the productivity can be further improved by eliminating the need for the drying step.
- the content of the organic solvent is more preferably 3 mass% or less.
- the viscosity ⁇ 1 of the active energy ray-curable adhesive at a temperature of 30°C and a shear rate of 300s- 1 is preferably 0.1 Pa ⁇ s or more and 20 Pa ⁇ s or less.
- the conditions of the temperature and the shear rate are assumed to be the temperature at the time of applying the adhesive and the shear rate when the adhesive is transferred onto the first substrate film and the ink having been transferred to the first substrate film.
- the viscosity ⁇ 1 is more preferably 10 Pa ⁇ s or less.
- the ratio ⁇ 1/ ⁇ of the viscosity ⁇ 1 of the active energy ray-curable adhesive to the viscosity ⁇ of the ink is preferably 0.01 or more and 1.0 or less.
- the adhesive can be applied to the uncured ink with good appearance.
- the viscosity ratio ⁇ 1/ ⁇ to 1.0 or less back trapping can be suppressed. By suppressing back trapping, the coating film of the adhesive can be uniformly formed, and adhesion as a laminate can also be improved.
- the above-described resin and monomer having an ethylenically unsaturated double bond may be used for the ink and the adhesive. Further, the viscosity can be controlled by using a compound having all or any of the following characteristics as a monomer having an ethylenically unsaturated double bond that dissolves the resin used for the adhesive, and appropriately adjusting the proportion thereof.
- the viscosity ⁇ 1 of the active energy ray-curable adhesive in the present invention can be measured by the same method as in the above-described ink.
- the viscosity ⁇ 1 of the active energy ray-curable adhesive can be adjusted to fall within the above-described range by, for example, using the above-described preferable resin and the compound having an ethylenically unsaturated double bond, and setting the molecular weight of the resin and the contents of the resin and the compound having an ethylenically unsaturated double bond to the above-described preferable ranges.
- the non-solvent isocyanate-curing adhesive preferably contains an isocyanate-curing resin and a compound having an ethylenically unsaturated double bond.
- the adhesive can be applied to the uncured ink with good appearance. In addition, the flexibility of the cured film of the adhesive can be moderately improved.
- the non-solvent isocyanate-curing adhesive contains a compound having an ethylenically unsaturated double bond, the viscosity of the non-solvent isocyanate-curing adhesive can be easily adjusted to a range suitable for processing, thus making it possible to improve the appearance of the laminated film.
- the adhesive can be cured by an active energy ray.
- the isocyanate-curing resin contains at least a polyol compound and a polyisocyanate compound.
- polyol compound examples include polyether polyol, polyester polyol, and polycarbonate polyol. Two or more of these may be contained. Among them, polyether polyol and polyester polyol are preferable from the viewpoint of productivity. From the viewpoint of improving the leveling property of the coating film of the non-solvent isocyanate-curing adhesive, polyether polyol is more preferable, and from the viewpoint of improving the heat resistance in high temperature sterilization applications, polyester polyol is more preferable.
- polyisocyanate examples include compounds having an aromatic isocyanate, an aliphatic isocyanate, an alicyclic isocyanate or the like at the terminal thereof. Two or more of these may be used. Among them, from the viewpoint of safety, a compound having an aliphatic isocyanate or an alicyclic isocyanate at the terminal thereof is preferable, and from the viewpoint of adjusting the reaction rate and viscosity, a compound having an aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic alicyclic diisocyanate at the terminal thereof is more preferable.
- Examples of the isocyanate-curing resin include a combination of a polyether polyol as a polyol compound and an aromatic polyisocyanate as a polyisocyanate, such as "TAKELAC” (registered trademark) A-244B/"TAKENATE” (registered trademark) A-244A, "TAKELAC” (registered trademark) A-246B/"TAKENATE” (registered trademark) A-246A, “TAKELAC” (registered trademark) A-248B/"TAKENATE” (registered trademark) A-246A manufactured by Mitsui Chemicals, Inc., and "EA-370A/EA-370B” manufactured by Toyo-Morton, Ltd.; and a combination of a polyester polyol as a polyol compound and an aliphatic, alicyclic, or aromatic alicyclic polyisocyanate as a polyisocyanate, such as "TAKELAC” (registered trademark) A
- Examples of the compound having an ethylenically unsaturated double bond include monomers, oligomers, and resins having an ethylenically unsaturated double bond.
- Urethane (meth)acrylate is more preferable from the viewpoint of compatibility with the isocyanate-curing resin.
- the urethane (meth)acrylate those exemplified as the urethane (meth)acrylate in the ink are preferable.
- Examples of the resin having an ethylenically unsaturated double bond include an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, a rosin-modified maleic acid resin, a rosin-modified acrylic resin, and a polyurethane resin. Two or more of these may be contained. Among them, an acrylic resin, a styrene acrylic resin, and a styrene maleic acid resin are preferable from the viewpoint of ease of synthesis, adhesion to the ink, the strength of the coating film, and the like.
- the monomer having an ethylenically unsaturated double bond preferably has two or more ethylenically unsaturated double bonds in one molecule because it has high curability.
- the number of ethylenically unsaturated double bonds in one molecule is preferably 6 or less, and more preferably 4 or less from the viewpoint of improving the flexibility of the cured film of the adhesive and improving the adhesiveness of the adhesive to the second substrate before the lamination step.
- those exemplified as the monomer having an ethylenically unsaturated double bond in the active energy ray-curable adhesive are preferable.
- the total content of the compound having an ethylenically unsaturated double bond in the non-solvent isocyanate-curing adhesive is preferably 1 mass% or more and 30 mass% or less.
- the total content of the compound having an ethylenically unsaturated double bond refers to, when the adhesive contains only one of the monomer, oligomer, and resin having an ethylenically unsaturated double bond, the total content of the one of these, and when the adhesive contains two or more of these, the total contents of the two or more of these.
- the total content thereof is more preferably 5 mass% or more.
- adhesion between the ink and the second substrate after the isocyanate-curing component is cured by aging can be further improved.
- the non-solvent isocyanate-curing adhesive may further contain a leveling agent, an extender pigment, and the like as necessary.
- the viscosity ⁇ 2 of the non-solvent isocyanate-curing adhesive at a temperature of 30°C and a shear rate of 300s- 1 is preferably 1 Pa ⁇ s or more, and preferably 20 Pa ⁇ s or less.
- the viscosity ⁇ 2' of the non-solvent isocyanate-curing adhesive at a temperature of 80°C and a shear rate of 300s -1 is preferably 0.05 Pa ⁇ s or more, and preferably 5 Pa ⁇ s or less.
- the conditions of the temperature and the shear rate are assumed to be the temperature range of 30 to 80°C at the time of applying the adhesive and the shear rate when the adhesive is transferred onto the first substrate film and the ink having been transferred to the first substrate film.
- the adhesive By setting the viscosity ⁇ 2 to 1 Pa ⁇ s or more, the adhesive can be applied to the uncured ink with good appearance, and the adhesiveness of the adhesive to the second substrate after the curing step and before the lamination step can be improved.
- the viscosity ⁇ 2 is more preferably 5 Pa ⁇ s or more.
- the viscosity ⁇ 2 by setting the viscosity ⁇ 2 to 20 Pa ⁇ s or less, the leveling property can be improved.
- the viscosity ⁇ 2 is more preferably 15 Pa ⁇ s or less.
- the adhesive By setting the viscosity ⁇ 2' to 0.05 Pa ⁇ s or more, the adhesive can be applied to the uncured ink with good appearance, and the adhesiveness of the adhesive to the second substrate after the curing step and before the lamination step can be improved.
- the viscosity ⁇ 2' is more preferably 0.08 Pa ⁇ s or more.
- the leveling property can be improved.
- the ratio ⁇ 2/ ⁇ of the viscosity ⁇ 2 of the non-solvent isocyanate-curing adhesive to the viscosity ⁇ of the ink is preferably 0.01 or more and 0.50 or less.
- the viscosity ratio ⁇ 2/ ⁇ is 0.01 or more, the adhesive can be applied to the uncured ink with good appearance.
- the viscosity ratio ⁇ 2/ ⁇ is 0.50 or less, the occurrence of orange peel or the like can be suppressed in the application of the adhesive.
- the above-described ink and the adhesive containing the above-described resin and compound having an ethylenically unsaturated double bond may be used. Further, the viscosity can be controlled by using a compound having all or any of the following characteristics as a monomer having an ethylenically unsaturated double bond, and appropriately adjusting the proportion thereof.
- the viscosities ⁇ 2 and ⁇ 2' of the active energy ray-curable adhesive in the present invention can be measured by the same method as the viscosity of the ink described above.
- the viscosities ⁇ 2 and ⁇ 2' of the non-solvent isocyanate-curing adhesive can be adjusted to fall within the above-described ranges by, for example, using the above-described preferable isocyanate-curing adhesive and the compound having an ethylenically unsaturated double bond, and setting the content of the compound having an ethylenically unsaturated double bond to the above-described preferable range.
- the first aspect of the method for producing a laminated film of the present invention includes a printing step, an adhesive application step, a lamination step, and a curing step in this order.
- the printing method is preferably offset printing (lithographic printing) or flexographic printing that does not require the drying step and enables a plurality of times of laminations of uncured ink (wet-on-wet printing).
- offset printing is more preferable from the viewpoint of easily suppressing back trapping of the ink
- waterless offset printing is still more preferable from the viewpoint that contamination of the ink with a trace amount of moisture does not occur because the offset printing does not require a dampening solution, and radicals generated by irradiation with an active energy ray can be efficiently used for a curing reaction.
- an active energy ray-curable adhesive is applied in-line to a printed material obtained by applying the ink to the first substrate by the above-described printing step.
- a method for applying the adhesive offset printing or flexographic printing is preferable because the adhesive is applied onto the uncured ink. Flexographic printing is more preferable because it is easy to increase the film thickness of the adhesive and it is suitable for applying a material having a relatively low viscosity.
- the application temperature of the adhesive is preferably 20°C to 40°C in order to maintain favorable viscosity and application appearance at the time of application.
- Examples of the printing press preferably used in the printing step and the adhesive application step include a center drum printing press "CI8" (manufactured by COMEXI).
- a coater having an existing active energy ray curing unit may be connected to the printing press.
- the second substrate is bonded and laminated, with a nip roll, to the laminate obtained by sequentially applying the ink and the adhesive to the first substrate.
- the nip pressure is preferably 0.1 MPa or more and 0.6 MPa or less.
- the nip roll temperature is preferably 40°C or more and 80°C or less.
- the ink and the active energy ray-curable adhesive on the first substrate film can be quickly cured by irradiation with an active energy ray.
- the active energy ray used may be any ray as long as the ray has an excitation energy necessary for the curing reaction, and examples thereof preferably include electron beams and ultraviolet rays.
- the ink can be cured without blending a photopolymerization initiator in the ink.
- the electron beam is particularly suitable for applications such as pharmaceutical packaging and food packaging in which migration of a low molecular weight compound to contents and odor peculiar to the initiator are avoided.
- the curability of the ink and/or the adhesive can be improved, which is preferable.
- the first aspect in the case of performing irradiation with an electron beam in a state where the first substrate and the second substrate are laminated, when electron beams are applied from both surfaces of the laminate, electron beams required for only curing the ink and/or the adhesive can be applied even by irradiation with electron beams at a low acceleration voltage. It is therefore possible to suppress deterioration of the substrate due to the electron beam.
- the active energy ray When the active energy ray is applied from only one of the first substrate film side and the second substrate side, it is preferable to apply the active energy ray from the side where the thickness is small or the side where the specific gravity of the substrate is small (when an aluminum foil is used for the second substrate, a side that is not an aluminum foil) from the viewpoint of more effectively proceeding the curing of the ink with the active energy ray.
- a substrate having a relatively large change in physical properties due to the electron beam such as a polypropylene film
- an electron beam device emitting an energy ray of 100 to 500 keV is preferably used.
- the irradiation dose of the electron beam is preferably 10 kGy or more from the viewpoint of improving the curability of the ink and the active energy ray-curable adhesive.
- the irradiation dose of the electron beam is preferably 80 kGy or less from the viewpoint of suppressing deterioration and discoloration of the first substrate film and the second substrate.
- the acceleration voltage contributing to the penetration depth of the electron beam is preferably 80 kV or more and 300 kV or less.
- the acceleration voltage is 80 kV or more, the electron beam can be stably generated.
- the acceleration voltage is 300 kV or less, more preferably 150 kV or less, a change in physical properties of the substrate film can be suppressed.
- an ultraviolet lamp such as a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or a light emitting diode (LED) is preferably used.
- a light emitting diode that emits a bright line having a wavelength of 350 to 420 nm is preferable from the viewpoint of power saving and cost reduction.
- the elastic modulus of the coating film of the active energy ray-curable adhesive after curing is preferably 5 MPa or more, and more preferably 10 MPa or more from the viewpoint of improving the flexibility and strength of the coating film.
- the elastic modulus of the coating film of the active energy ray-curable adhesive after curing is preferably 600 MPa or less, and more preferably 500 MPa or less from the viewpoint of suppressing generation of cracks and the like.
- the elastic modulus of the coating film is measured by a nanoindenter.
- the second aspect of the method for producing a laminated film of the present invention includes a printing step, an adhesive application step, a curing step, and a lamination step in this order.
- the printing step and the lamination step are the same as those in the first aspect.
- the non-solvent isocyanate-curing adhesive is applied in-line to the printed material obtained by applying the ink to the first substrate by the printing step without passing through the winding step.
- the method for applying the adhesive include the methods exemplified in the first aspect, and flexographic printing is preferable.
- the application temperature of the adhesive is preferably 20°C to 80°C in order to maintain favorable viscosity and application appearance at the time of application.
- Examples of the printing press preferably used in the printing step and the adhesive application step include those exemplified in the first aspect.
- the curing step will be described.
- the ink on the first substrate film can be quickly cured by irradiation with an active energy ray.
- the initial adhesion strength can be improved by semi-curing the non-solvent isocyanate-curing adhesive to increase the apparent molecular weight thereof.
- the second substrate since the second substrate is not irradiated with an electron beam, a change in physical properties of the second substrate due to the electron beam can be prevented.
- the active energy ray used may be any ray as long as the ray has an excitation energy necessary for the curing reaction, and examples thereof preferably include electron beams and ultraviolet rays.
- the initial peel strength of the laminate obtained by the method for producing a laminated film of the present invention is preferably 0.5 N or more, more preferably 0.8 N or more, more preferably 1.0 N or more, still more preferably 1.5 N or more from the viewpoint of preventing appearance defects in post-processing.
- the peel strength after aging of the laminate obtained in the second aspect is preferably 1.5 N or more, more preferably 2.0 N or more, and still more preferably 3.0 N or more from the viewpoint of maintaining good strength as a packaging material.
- the peeling strength of the laminate is measured in the section (8) of the evaluation method in Examples described later.
- the weight average molecular weight of the resin used in Examples and Comparative Examples is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase.
- Each resin was added to tetrahydrofuran so as to have a resin concentration of 0.25 mass%, and dissolved by stirring at a rotation speed of 100 rpm for 5 minutes using a shaker MIX-ROTAR VMR-5 (manufactured by AS ONE Corporation).
- the obtained solution was filtered with a 0.2 um filter Z227536-100EA (manufactured by SIGMA), and the filtrate was used as a measurement sample.
- Detection was performed using an RI detector built in a gel permeation chromatography apparatus HLC-8220 (manufactured by Tosoh Corporation).
- TSKgel SuperHM-H manufactured by Tosoh Corporation
- TSKgel SuperHM-H manufactured by Tosoh Corporation
- TSKgel SuperH 2000 manufactured by Tosoh Corporation
- the injection amount was 10 ⁇ L
- the analysis time was 30 minutes
- the flow rate was 0.4 mL/min
- the column temperature was 40°C.
- the weight average molecular weight of the resin was calculated from the calibration curve created using the polystyrene standard substance.
- the acid value of the resin was determined according to the neutralization titration in Section 3.1 of the test method of JIS K 0070: 1992.
- the iodine value of the resin was determined by the method described in Section 6.0 of the test method of JIS K 0070: 1992.
- the hydroxyl value of the monomer was measured according to the neutralization titration of Section 7.1 of the test method of JIS K 0070: 1992.
- the viscosity of the ink used in Examples and Comparative Examples was measured by the following procedure using a dynamic viscoelasticity measuring device Pyhsia MCR301 (manufactured by Anton Paar GmbH) using a cone plate jig having a cone plate with a diameter of 40 mm and an inclination angle of 1.00° and a lower plate, and having a gap between the cone plate and the lower plate of 81 ⁇ m.
- a dynamic viscoelasticity measuring device was heated to 30°C in advance, 0.7 mL of ink was placed between the heated cone plate and lower plate, and the cone plate jig is set at the measurement position and then allowed to stand at 30°C for 3 minutes.
- the viscosity at a shear rate of 300s -1 was determined from an approximate curve of the shear rate and the viscosity obtained by measuring the viscosity of the ink while the shear rate is continuously changed logarithmically in the range of the shear rate of 1 to 490s -1 at a temperature of 30°C.
- the viscosity ⁇ 2' of the non-solvent isocyanate-curing adhesive used in Examples and Comparative Examples was measured in the same manner as in the viscosities ⁇ 1 and ⁇ 2 except that the preheating temperature and the measurement temperature of the device were set to 80°C.
- a laminated film was produced in the same manner as in Examples and Comparative Examples except that a PET film "EMBLET” (registered trademark) PET 12 um (manufactured by UNITIKA Ltd.) was used instead of the film A as the first substrate. Since the ink in the obtained laminated film was subjected to a curing step under the same conditions as those in Examples and Comparative Examples, the curability of the ink in the laminated film obtained in Examples and Comparative Examples was evaluated from the ink in the laminated film obtained here.
- EMBLET registered trademark
- PET 12 um manufactured by UNITIKA Ltd.
- the obtained laminated film was allowed to stand at 40°C for 72 hours, that is, aged. Then, the PET film as the first substrate was peeled off, and the exposed surface of the ink cured product was rubbed with a cloth (No. 6 canvas) immersed in methyl ethyl ketone. The presence or absence of coloring of the cloth with the ink was visually observed. The curability of the ink was evaluated according to the following criteria from the number of reciprocations until the cloth was colored.
- a section having a width of 15 mm and a length of 50 mm was cut out from the laminated film obtained in Examples and Comparative Examples.
- the first substrate film and the second substrate were respectively held with upper and lower chucks of a TENSILON universal material testing instrument RTG-1210 (manufactured by A & D Company, Limited), and a tensile test was performed at a test speed of 300 mm/min to measure a load value at a first maximum point. Measurement was performed three times, and the average value of the measurements was taken as the initial peel strength. Further, the section after the tensile test were visually observed, and the peeling mode was specified.
- the laminated film obtained in Examples and Comparative Examples was allowed to stand at a temperature of 40°C for 72 hours, that is, aged. Then, the peel strength after aging was measured by the same method, and the adhesion was evaluated. A case where the peel strength after aging was 2.0 N or more, or a case where the fracture mode was film breakage was evaluated as having good adhesion.
- the productivity was also evaluated from the initial peel strength and the peel strength after aging according to the following criteria.
- the leveling property was visually observed from gloss and the presence or absence of ink voids in the solid part immediately after the ink was transferred to the first substrate film A, and the print appearance was evaluated according to the following criteria.
- the reflection density of the solid part after the printing step and before the adhesive application step and the reflection density of the solid part of the obtained laminated film were measured using a reflection densitometer ("SpectroEye" manufactured by GretagMacbeth LLC) in the measurement mode of status E, and the presence or absence of back trapping was evaluated from the difference between the reflection densities.
- a coated paper was used as a standard for the reflection density of 0.
- the color density change is 0.1 or more and less than 0.3, and interlayer delamination, bubbles, and the like are hardly observed
- the color density change is 0.3 or more, or interlayer delamination, bubbles, or the like is observed.
- a resin having an ethylenically unsaturated double bond and a hydrophilic group (hydroxyl group and carboxyl group) was obtained by an addition reaction in which 0.55 equivalents of glycidyl methacrylate were combined with carboxyl groups of a copolymer of 25 mass% of methyl methacrylate, 25 mass% of styrene, and 50 mass% of methacrylic acid, and the obtained resin was used as a resin 1.
- the obtained resin 1 had a weight average molecular weight of 34,000, an acid value of 105 mgKOH/g, and an iodine value of 2.0 mol/kg.
- a resin which was a copolymer of 25 mass% of methyl methacrylate, 25 mass% of styrene, and 50 mass% of methacrylic acid was used as a resin 2.
- the resin 2 has neither a hydrophilic group nor an ethylenically unsaturated double bond.
- the weight average molecular weight of the resin 2 was 30,000.
- urethane acrylate 1 An oligomer having two ethylenically unsaturated double bonds at terminals thereof was used as a urethane acrylate 1, and the oligomer was obtained from alicyclic diisocyanate (IPDI), polyether polyol (polytetramethylene ether glycol), and 2-hydroxyethyl acrylate.
- IPDI alicyclic diisocyanate
- polyether polyol polytetramethylene ether glycol
- 2-hydroxyethyl acrylate 2-hydroxyethyl acrylate.
- the weight average molecular weight of the urethane acrylate 1 was 3,300.
- urethane acrylate 2 An oligomer having two ethylenically unsaturated double bonds at terminals thereof was used as a urethane acrylate 2, and the oligomer was obtained from alicyclic diisocyanate (IPDI), polyether polyol (polytetramethylene ether glycol), and 2-hydroxyethyl acrylate.
- IPDI alicyclic diisocyanate
- polyether polyol polytetramethylene ether glycol
- 2-hydroxyethyl acrylate 2-hydroxyethyl acrylate.
- the weight average molecular weight of the urethane acrylate 2 was 13,000.
- Tricyclodecane dimethanol diacrylate "Miramer” (registered trademark) M262 (manufactured by MIWON) was used.
- the hydroxyl value of the monomer 2 was 0 mgKOH/g.
- Resin 1 11.7 mass%, monomer 1: 42.1 mass%, monomer 2: 25.1 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 3.0 mass%.
- Resin 1 10.5 mass%, urethane acrylate 1: 10.0 mass%, monomer 1: 40.4 mass%, monomer 2: 20.0 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 1.0 mass%.
- Resin 1 9.7 mass%, monomer 1: 43.1 mass%, monomer 2: 26.1 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 3.0 mass%.
- Resin 2 18.0 mass%, monomer 1: 30.5 mass%, monomer 2: 30.4 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 3.0 mass%.
- the resin 1, the monomer 1, and the monomer 2 were blended in the compositions shown in Table 1, and the mixture was passed through a three roll mill “EXAKT” (registered trademark) M-80S (manufactured by Exakt Technologies.) five times with the setting "Gap 1" in the apparatus to obtain an active energy ray-curable adhesive.
- EXAKT registered trademark
- M-80S manufactured by Exakt Technologies.
- the ink A was transferred onto the first substrate film A so that the application amount was 1.0 g/m 2 to form an ink coating film (printing step).
- a flexographic printing unit of the center drum printing press "CI8” manufactured by COMEXI
- an adhesive A was applied onto the ink coating film so that the application amount was 2.0 g/m 2 (adhesive application step), and the second substrate film B was laminated thereon using a nip roll (lamination step).
- the obtained laminate was irradiated with an electron beam from the first substrate film side under the conditions of an acceleration voltage of 110 kV and an irradiation dose of 30 kGy (curing step) to obtain a laminated film with the first substrate film A, the ink A, the active energy ray-curable adhesive, and the second substrate film B laminated in this order.
- the evaluation results of the obtained laminated film are shown in Table 1.
- Laminated films were produced in the same manner as in Example 1 except that the composition and ink of the active energy ray-curable adhesive were changed as shown in Table 1. The evaluation results of the obtained laminated films are shown in Table 1.
- a laminated film was produced in the same manner as in Example 1 except that the composition and ink of the active energy ray-curable adhesive were changed as shown in Table 1, and an electron beam was applied from both sides of the first substrate film side and the second substrate film side using an electron beam irradiation unit under the conditions of an acceleration voltage of 110 kV and an irradiation dose of 30 kGy.
- the evaluation results of the obtained laminated films are shown in Table 1.
- the ink A was transferred to the first substrate film A by the same method as in Example 1 (printing step), and electron beam irradiation was performed under the same conditions as in Example 1 (curing step) to obtain a laminate of the first substrate film A/cured film of the ink A.
- a mixture of a solvent-containing adhesive "TAKELAC” (registered trademark) A-969V/"TAKENATE” (registered trademark) A-5 manufactured by Mitsui Chemicals, Inc. at a mass ratio of 3/1 was applied onto the cured film of the ink A using a bar coater so that the application amount was 2.0 g/m 2 , and dried at 80°C for 1 minute (adhesive application step).
- the second substrate film B was laminated using a hand roller (lamination step) to obtain a laminated film with the first substrate film A, the ink A, the adhesive, and the second substrate film B laminated in this order.
- the evaluation results of the obtained laminated films are shown in Table 1.
- the ink A was transferred onto the substrate film A so that the application amount was 1.0 g/m 2 to form an ink coating film (printing step).
- the second substrate film B was laminated using a nip roll to obtain a laminated film.
- the evaluation results of the obtained laminate are shown in Table 2.
- TAKELAC (registered trademark) A-670 B/"TAKENATE” (registered trademark) A-670A” (mass ratio: 5/10) as isocyanate-curing resins, and the resin 1 were blended in the compositions shown in Table 2 to obtain a non-solvent isocyanate-curing adhesive.
- TAKELAC registered trademark
- A-670B and 10 parts by mass of the resin 1 were mixed by passing these materials through a three roll mill "EXAKT” (registered trademark) M-80S (manufactured by Exakt Technologies.) five times with the setting "Gap 1" in the apparatus.
- a laminated film was obtained in the same manner as in Example 7 except that the non-solvent isocyanate-curing adhesive was used.
- the evaluation results of the obtained laminated film are shown in Table 2.
- TAKELAC (registered trademark) A-670B/"TAKENATE” (registered trademark) A-670A (mass ratio: 5/10) as isocyanate-curing resins, and urethane acrylate 1 or 2 were blended in the compositions shown in Table 2 to obtain each non-solvent isocyanate-curing adhesive.
- 10 parts by mass of urethane acrylate 1 or 2 was added to 90 parts by mass of a mixture of "TAKELAC” (registered trademark) A-670B/"TAKENATE” (registered trademark) A-670A at a mass ratio of 5/10, and the mixture was manually shaken and stirred to obtain each non-solvent isocyanate-curing adhesive.
- the ink A was transferred to the first substrate film A by the same method as in Example 1 (printing step), and electron beam irradiation was performed under the same conditions as in Example 1 (curing step) to obtain a laminate of the first substrate film A/cured film of the ink A.
- TAKELAC non-solvent isocyanate-curing adhesive
- A-244B/"TAKENATE registered trademark
- A-244A manufactured by Mitsui Chemicals, Inc. at a mass ratio of 5/10 was applied onto the cured film of the ink A using a bar coater so that the application amount was 2.0 g/m 2 (adhesive application step).
- the second substrate film B was laminated using a hand roller (lamination step) to obtain a laminated film with the first substrate film A, the ink A, the adhesive, and the second substrate film B laminated in this order.
- the evaluation results of the obtained laminated films are shown in Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
An object of the present invention is to provide a method for producing a laminated film, the method capable of producing a laminated film excellent in curability of an ink and adhesion between the ink and a second substrate with high productivity.
The present invention is a method for producing a laminated film, the method including: a printing step of applying an active energy ray-curable printing ink to a first substrate film formed of at least a plastic film; an adhesive application step of applying an adhesive; and a lamination step of laminating a second substrate, the steps being performed in this order in-line, the method further including a curing step of irradiating the active energy ray-curable printing ink with an active energy ray to cure the active energy ray-curable printing ink after at least the adhesive application step.
Description
- The present invention relates to a method for producing a laminated film, the method including: a printing step of applying an active energy ray-curable printing ink to a first substrate film formed of at least a plastic film; an adhesive application step of applying an adhesive; and a lamination step of laminating a second substrate, the steps being performed in this order in-line.
- Lithographic printing (offset printing) is a printing system widely used as a system capable of inexpensively supplying a large volume of printed material at high speed. Conventionally, the lithographic system has been mainly applied to printing on paper, but in recent years, application to soft packaging printing for printing on a thin plastic film has been studied mainly for packaging applications such as daily goods, foodstuffs, and pharmaceuticals.
- In recent years, active energy ray-curable lithographic inks that are instantaneously cured by irradiation with an active energy ray such as a mercury lamp, a metal halide lamp, a light emitting diode, or an electron beam are widely known in many fields from the viewpoints of equipment, safety, environment, and productivity. Such an active energy ray-curable lithographic ink is considered to be a material suitable for printing on a plastic film having poor heat resistance because it can be cured at room temperature in a short time. However, along with an increase in the printing speed and reduction in the exposure amount due to power saving, curing of the ink is insufficient in some cases. In view of the above problem, as a lithographic ink having both highly sensitive active energy ray curability and water washability and excellent scumming resistance during printing and water resistance of a cured film, there has been proposed a lithographic ink containing (a) a pigment and (b) a resin having an ethylenically unsaturated group and a hydrophilic group (see, for example, Patent Document 1). In the above-described packaging applications and the like, another plastic film, a metal foil, a hot-melt film (sealant) or the like is generally bonded to the obtained printed material from the viewpoint of protecting contents, improving impact resistance, imparting heat sealability and the like.
- Meanwhile, as a method for producing a packaging material using a thin plastic film as a substrate, there have been proposed a method including printing a pattern on a substrate, curing an ink by energy ray irradiation, and laminating a heat seal layer on the substrate with an adhesive interposed therebetween (see, for example, Patent Document 2), a method including a step of applying an ink composition to a
transparent substrate 1, and drying and curing the ink composition to obtain an ink layer, a step of applying a specific adhesive composition onto the ink layer to form a precursor of an adhesive layer, a step of stacking asubstrate 2 onto the precursor of the adhesive layer, and a step of curing the precursor of the adhesive layer to form the adhesive layer (see, for example, Patent Document 3), and the like. -
- Patent Document 1: International Publication No.
2017/047817 - Patent Document 2:
Japanese Patent Laid-open Publication No. 2005-329983 - Patent Document 3:
Japanese Patent Laid-open Publication No. 2018-27658 - In the production of a laminated film in which another substrate is laminated on a printed material having a plastic film as a substrate,
Patent Documents 2 to 3 disclose a method of laminating a second substrate to a cured ink layer by using an isocyanate-curing adhesive in off-line. In such a method, an active energy ray-curable printing ink is preferably used from the viewpoint of reducing an organic solvent, but there is a problem that the curability of the ink and adhesion between the ink and the plastic film is insufficient. Moreover, a long aging process such as processing at 40°C for 3 days is required for curing the isocyanate-curing adhesive, and there is a problem in productivity. - Therefore, an object of the present invention is to solve the problems of the prior art, and to provide a method for producing a laminated film, in which a laminated film excellent in curability of the ink and adhesion between the ink and the second substrate can be produced with high productivity.
- The present inventors have paid attention to the fact that when the surface of the ink is exposed to oxygen in the process of curing the ink by an active energy ray, the curability of the ink and adhesion between the ink and the plastic film become insufficient, and have arrived at the present invention.
- That is, the present invention is a method for producing a laminated film, the method including: a printing step of applying an active energy ray-curable printing ink to a first substrate film formed of at least a plastic film; an adhesive application step of applying an adhesive; and a lamination step of laminating a second substrate, the steps being performed in this order in-line, the method further including a curing step of irradiating the active energy ray-curable printing ink with an active energy ray to cure the active energy ray-curable printing ink after at least the adhesive application step.
- According to the method for producing a laminated film of the present invention, a laminated film excellent in curability of the ink and adhesion between the ink and the second substrate can be produced with high productivity.
-
-
Fig. 1 is a schematic view showing an example of a first aspect of a method for producing a laminated film of the present invention. -
Fig. 2 is a schematic view showing an example of a second aspect of the method for producing a laminated film of the present invention. - Hereinafter, the present invention will be specifically described.
- A method for producing a laminated film of the present invention includes a printing step of applying an active energy ray-curable printing ink (hereinafter, may be simply referred to as "ink") to a first substrate film formed of at least a plastic film, an adhesive application step of applying an adhesive, and a lamination step of laminating a second substrate, the steps being performed in this order in-line, the method further including a curing step of irradiating the active energy ray-curable printing ink with an active energy ray after at least the adhesive application step. The laminated film in the present invention has at least a cured product of the ink, a cured product of the adhesive, and the second substrate film on the first substrate film. The cured product of the ink only needs to be provided at a necessary position according to the pattern, and does not need to be provided on the entire surface of the laminated film.
- A first aspect of the method for producing a laminated film of the present invention employs an active energy ray-curable adhesive as an adhesive in the adhesive application step, and includes the printing step, adhesive application step, lamination step, and curing step described above in this order. That is, the first aspect of the method for producing a laminated film of the present invention is a method including applying an ink and an adhesive, laminating a second substrate thereon, and then curing the ink and the adhesive by an active energy ray.
- A second aspect of the method for producing a laminated film of the present invention employs a non-solvent isocyanate adhesive as an adhesive in the adhesive application step, and includes the printing step, adhesive application step, curing step, and lamination step described above in this order. That is, the second aspect of the method for producing a laminated film of the present invention is a method including applying an adhesive onto an ink, curing the ink by an active energy ray, and then laminating a second substrate thereon. In both aspects, by continuously performing the printing step to the lamination step or the curing step in a series of production processes, that is, in-line, the lead time is reduced, thus making it possible to improve the productivity. In addition, the processing loss generated in the lamination step can be reduced as compared with the off-line production in which the printing step and the lamination step are discontinuously performed. Further, when the ink is cured by an active energy ray, the presence of the adhesive and/or the second substrate on the surface of the ink suppresses insufficient curing of the ink due to exposure of the surface of the ink to oxygen. This makes it possible to improve the adhesion between the second substrate and the ink, and the curability of the ink.
-
Fig. 1 shows a schematic view of an example of the first aspect of the method for producing a laminated film of the present invention. An ink is applied to afirst substrate film 1 by anoffset printing unit 2 of a center drum lithographic printing press (printing step). Subsequently, on the same cylinder, an active energy ray-curable adhesive is applied by aflexographic printing unit 3 of the center drum lithographic printing press (adhesive application step), and asecond substrate 5 is laminated thereon using a nip roll 4 (lamination step). Then, the ink and the active energy ray-curable adhesive are simultaneously cured by irradiation with an active energy ray by an electron beam irradiation device 6 (curing step). -
Fig. 2 shows a schematic view of an example of the second aspect of the method for producing a laminated film of the present invention. An ink is applied to afirst substrate film 1 by anoffset printing unit 2 of a center drum lithographic printing press (printing step). Subsequently, on the same cylinder, a non-solvent isocyanate-curing adhesive is applied by aflexographic printing unit 3 of the center drum lithographic printing press (adhesive application step), the ink is irradiated with an active energy ray by an electronbeam irradiation device 6 via the non-solvent isocyanate-curing adhesive (curing step) to cure the ink, and then asecond substrate 5 is laminated thereon using a nip roll 4 (lamination step). - The first substrate film is formed of a plastic film, and imparts the strength to the laminated film to withstand tension and the like generated in the printing step. Examples of the plastic film include an oriented polyester film, an oriented polyamide film, an oriented polypropylene (OPP) film, a cast polypropylene film (CPP), and a polyethylene film. The plastic film can be appropriately selected among them according to the required properties such as the leveling property of the ink, appearance quality, barrier property for protecting the contents, and the like, and two or more of these may be used. These plastic films may have an easily adhesive layer, an anchor layer, a metal vapor deposition layer, a metal oxide layer, and the like.
- The thickness of the first substrate film is preferably 50 um or less, and more preferably 30 um or less from the viewpoint of processability and cost.
- Examples of the second substrate include an oriented film, a metal film, and a hot-melt film (sealant film). Two or more of these may be used.
- By using an oriented film as the second substrate, the strength of the laminated film can be improved, thus making it possible to improve the effect of protecting the contents in packaging applications. Examples of the oriented film include an oriented polyamide film, an oriented polyester film, and an oriented polyolefin film. The oriented film may have a metal vapor deposition layer, a metal oxide layer, and the like. In packaging applications, the oriented film can suppress deterioration of the contents due to transmission of oxygen, water vapor, light, and the like to the inside.
- By using a metal film as the second substrate, it is possible to further suppress deterioration of the contents due to transmission of oxygen, water vapor, light, and the like to the inside. In addition, the metal film can suppress infiltration of the contents to the outer layer side thereof and suppress deterioration of the outer layer portion. Examples of the metal film include an aluminum foil.
- By using a hot-melt film as the second substrate, a pouch can be formed by thermally melting (heat-sealing) the laminated portion of the first substrate and the second substrate. Examples of the hot-melt film include a cast polypropylene film (CPP), a linear low density polyethylene film (LLDPE), and a low density polyethylene film (LDPE).
- In the case of the oriented film, the thickness of the second substrate is preferably 50 um or less, and more preferably 30 um or less from the viewpoint of processability and cost. In the case of the metal film, the thickness is preferably 20 um or less, and more preferably 12 um or less. In the case of the hot-melt film, the thickness is preferably 20 to 120 µm.
- The active energy ray-curable printing ink in the present invention refers to one containing a component having an ethylenically unsaturated double bond. The active energy ray-curable printing ink in the present invention preferably contains a resin and a compound having an ethylenically unsaturated double bond. When the active energy ray-curable printing ink contains the resin, fluidity suitable for the ink can be imparted to the active energy ray-curable printing ink, and scattering (misting) of the ink at the time of printing can be suppressed. Note that even a resin having an ethylenically unsaturated double bond is classified as the resin. Examples of the compound having an ethylenically unsaturated double bond include monomers and oligomers having an ethylenically unsaturated double bond. The molecular weight of the monomer is preferably less than 1,500. The oligomer refers to a polymer having a relatively low molecular weight, and the weight average molecular weight thereof is preferably 1,500 or more and 15,000 or less. The active energy ray-curable printing ink preferably contain a urethane (meth)acrylate as the oligomer having an ethylenically unsaturated double bond. Here, "(meth)acrylate" is a generic term including acrylate and methacrylate. When the active energy ray-curable printing ink contains urethane (meth)acrylate, the cohesive force of the ink can be improved by hydrogen bond interaction derived from a urethane bond. Therefore, it is possible to reduce the difference in viscosity between the ink and the adhesive and to suppress back trapping. Also in the second aspect, inclusion of urethane (meth)acrylate improves the affinity of the active energy ray-curable printing ink with the non-solvent isocyanate-curing adhesive, thus making it possible to further improve the adhesion between the ink and the second substrate. The active energy ray-curable printing ink may further contain another monomer having an ethylenically unsaturated double bond, a pigment, an acylphosphine oxide compound, or the like. Examples of the ink include the printing ink disclosed in International Publication No.
2020/235557 . - Examples of the resin contained in the ink include an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, a rosin-modified maleic acid resin, a rosin-modified acrylic resin, an epoxy resin, a polyester resin, a polyurethane resin, and a phenol resin. Two or more of these may be used. Among them, an acrylic resin, a styrene acrylic resin, and a styrene maleic acid resin are preferably used from the viewpoint of ease of synthesis, compatibility with other components, dispersibility of the pigment, and the like.
- The resin contained in the ink preferably has an ethylenically unsaturated double bond and a hydrophilic group. When the resin has an ethylenically unsaturated double bond, a crosslinked structure is formed by a reaction with a radical species in the curing step, so that the sensitivity of the ink to an active energy ray can be improved. In addition, a strong covalent bond is formed by a reaction with the acryloyl group of urethane (meth)acrylate, so that adhesion of the ink to the first substrate film and resistance of the laminated film to hot water treatment or the like can be improved. Further, in the first aspect, a strong covalent bond is formed by a reaction with the acryloyl group contained in the active energy ray-curable adhesive, so that adhesion of the ink to the second substrate can be further improved. On the other hand, when the resin has a hydrophilic group and the active energy ray-curable printing ink contains urethane (meth)acrylate, the cohesive force of the ink is increased by strong interaction with a urethane bond. As a result, the resistance of the laminated film to hot water treatment or the like and the scumming resistance of the ink can be improved, thus making it possible to suppress back trapping. Here, the term "scumming resistance" means that a phenomenon (scumming) in which the ink is deposited on the printing plate and transferred to the first substrate film hardly occurs in a non-image area to which the ink is not intended to be transferred. In addition, the term "back trapping" refers to a phenomenon in which the viscosity of the adhesive becomes larger than that of the ink, and the ink is transferred to the adhesive side.
- Examples of the hydrophilic group include a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfo group, and a phosphate group. Two or more of these may be contained. When the active energy ray-curable printing ink contains urethane (meth)acrylate, among these, a carboxyl group and a hydroxyl group which have good interaction with a urethane bond are preferable, and more preferably, the resin has a carboxyl group and a hydroxyl group.
- The acid value of the resin having an ethylenically unsaturated group, a carboxyl group, and a hydroxyl group is preferably 75 mgKOH/g or more, and preferably 150 mgKOH/g or less. Here, the acid value of the resin may be measured according to the neutralization titration in Section 3.1 of the test method of JIS K 0070: 1992. The iodine value of the resin having an ethylenically unsaturated group, a carboxyl group, and a hydroxyl group is preferably 1.5 mol/kg or more, and preferably 2.5 mol/kg or less. Here, the iodine value of the resin may be measured according to the method described in Section 6.0 of the test method of JIS K 0070: 1992.
- The resin having an ethylenically unsaturated group, a carboxyl group, and a hydroxyl group can be obtained, for example, by copolymerizing a monomer having a carboxyl group, a monomer having a hydroxyl group, and other monomers as necessary, and then adding an ethylenically unsaturated compound having a glycidyl group to the resulting copolymer.
- The weight average molecular weight of the resin is preferably 20,000 or more from the viewpoint of improving the resistance of the laminated film to hot water treatment or the like and the scumming resistance of the ink, and increasing the viscosity of the ink to suppress back trapping. On the other hand, the weight average molecular weight of the resin is preferably 50,000 or less from the viewpoint of improving the fluidity of the ink. Here, the weight average molecular weight of the resin refers to a value in terms of polystyrene calculated using gel permeation chromatography (GPC).
- The content of the resin in the ink is preferably 5 mass% or more, and more preferably 10.0 mass% or more from the viewpoint of easily adjusting the viscosity α described later to a preferable range described later. On the other hand, the content of the resin in the ink is preferably 40 mass% or less, and more preferably 15 mass% or less from the viewpoint of easily adjusting the viscosity α described later to a preferable range described later.
- The urethane (meth)acrylate can be obtained by a reaction of a polyol, an isocyanate, and a (meth)acrylate. More specifically, the urethane (meth)acrylate can be obtained, for example, by a method of adding a polyol to an addition reaction product of an isocyanate and a (meth)acrylate. Examples of the polyol include polyether polyol, polyester polyol, and polycarbonate polyol. The isocyanate is preferably, for example, alicyclic isophorone diisocyanate (IPDI) and hydrogenated xylylene diisocyanate from the viewpoint of heat resistance and safety. In addition, the isocyanate is preferably tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and xylylene diisocyanate (XDI) from the viewpoint of cost, except for applications in which there is a risk of elution into contents such as food to be heat-sterilized. The (meth)acrylate is preferably 2-hydroxyethyl acrylate.
- Since a segment derived from the polyol has high flexibility, the flexibility and shape conformity of the urethane (meth)acrylate are improved as the molecular weight of the polyol is larger, so that adhesion of the ink to the second substrate can be further improved. On the other hand, from the viewpoint of sensitivity to an active energy ray and curability, it is preferable that the molecular weight of the polyol is small and the ratio of the (meth)acrylate is high.
- In the present invention, the weight average molecular weight of the urethane (meth)acrylate is preferably 500 or more from the viewpoint of improving the sensitivity to an active energy ray and further improving the curability. On the other hand, the weight average molecular weight of the urethane (meth)acrylate is preferably 10,000 or less from the viewpoint of improving the scumming resistance and the transferability of the ink.
- The urethane (meth)acrylate preferably has two or more (meth)acrylates in one molecule, and more preferably two (meth)acrylates from the viewpoint of compatibility with other ink components and easily adjusting the viscosity α described later to a preferable range described later.
- The monomer having an ethylenically unsaturated double bond is preferably a (meth)acrylate having a hydroxyl group. Such a (meth)acrylate can improve the resistance of the laminated film to hot water treatment or the like by interaction with the hydrophilic group in the resin. Preferred examples of the (meth)acrylate having a hydroxyl group include pentaerythritol tri(meth)acrylate, diglycerin tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate.
- The content of the compound having an ethylenically unsaturated double bond in the ink is preferably 50 mass% or more, and more preferably 65 mass% or more from the viewpoint of easily adjusting the viscosity α described later to a preferable range described later. On the other hand, the content of the compound having an ethylenically unsaturated double bond in the ink is preferably 80 mass% or less from the viewpoint of easily adjusting the viscosity α described later to a preferable range described later. In particular, the content of the urethane (meth)acrylate is preferably 1 mass% or more in order to improve adhesion of the ink to the substrate, and is preferably 20 mass% or less from the viewpoint of compatibility with other ink components and easily adjusting the viscosity α described later to a preferable range described later.
- Examples of the pigment include an inorganic pigment and an organic pigment. The content of the pigment in the ink is preferably 15 mass% or more, and preferably 40 mass% or less in the case of a pigment having a specific gravity of 2 or less. The content of the pigment is preferably 40 mass% or more, and preferably 50 mass% or less in the case of a pigment having a specific gravity of more than 2.
- Since the acylphosphine oxide compound absorbs light in a long wavelength range of 350 nm or more, the acylphosphine oxide compound has high sensitivity even when the ink contains a pigment that absorbs or reflects ultraviolet light. In addition, the acylphosphine oxide compound has a photobleaching effect in which light absorption is lost after the reaction, and thus exhibits excellent internal curability. In particular, the acylphosphine oxide compound can improve the compatibility by being combined with a (meth)acrylate having a hydroxyl group, and improve the sensitivity of the ink to the active energy ray. Preferred examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide.
- The content of the acylphosphine oxide compound in the ink is preferably 5 mass% or more from the viewpoint of improving the sensitivity. On the other hand, the content of the acylphosphine oxide compound is preferably 10 mass% or less from the viewpoint of improving storage stability.
- The viscosity α of the ink at a temperature of 30°C and a shear rate of 300s-1 is preferably 10 Pa · s or more and 40 Pa · s or less. The conditions of the temperature and the shear rate are assumed to be the temperature at the time of printing and the shear rate when the ink is transferred to the first substrate film. By setting the viscosity α to 10 Pa · s or more, the scumming resistance can be improved. The viscosity α is more preferably 15 Pa · s or more, and still more preferably 20 Pa · s or more. On the other hand, by setting the viscosity α to 40 Pa · s or less, the transferability of the ink to the first substrate film and the leveling property can be improved. The viscosity α is more preferably 35 Pa · s or less, and still more preferably 30 Pa · s or less.
- Here, the viscosity α of the ink in the present invention can be measured using a dynamic viscoelasticity measuring device (rheometer) and a cone plate jig. The ink is placed between a cone plate and a lower plate, and the viscosity of the ink is measured from the torque applied to the cone plate when the cone plate rotates. The cone plate has a diameter of 40 mm and an inclination angle of 1°, and the gap between the cone plate and the lower plate is 81 um. The dynamic viscoelasticity measuring device is heated to 30°C in advance, the ink is placed on the lower plate, and the cone plate jig is set at the measurement position and then allowed to stand at 30°C for 3 minutes. The viscosity of the ink is measured while the shear rate is continuously changed logarithmically in the range of the shear rate of 1 to 490s-1 to obtain an approximate expression of the shear rate and the viscosity. The viscosity α at a shear rate of 300s-1 is determined from the approximate expression.
- The viscosity α of the ink can be adjusted to fall within the above-described range by, for example, using the above-described preferable resin, setting the contents of the resin and the compound having an ethylenically unsaturated double bond to the above-described preferable ranges, and using urethane (meth)acrylate as the compound having an ethylenically unsaturated double bond.
- As the adhesive, an active energy ray-curable adhesive or a non-solvent isocyanate-curing adhesive is preferable. These adhesives are excellent in productivity because they do not generally contain an organic solvent to such an extent that the drying step is required and thus the drying step is unnecessary. Here, the term "non-solvent" means that the content of the organic solvent is 5 mass% or less. The content of the organic solvent is preferably 3 mass% or less.
- The active energy ray-curable adhesive preferably contains a resin and a compound having an ethylenically unsaturated double bond. When the active energy ray-curable adhesive contains a resin, the adhesive can be applied to the uncured ink with good appearance. In addition, the flexibility of the cured film of the active energy ray-curable adhesive can be moderately improved. In addition, when the active energy ray-curable adhesive contains a compound having an ethylenically unsaturated double bond, the viscosity of the active energy ray-curable adhesive can be easily adjusted to a range suitable for processing, thus making it possible to improve the appearance of the laminated film. In addition, the adhesive can be cured by an active energy ray. Note that even a resin having an ethylenically unsaturated double bond is classified as the resin.
- The resin preferably contains an isocyanate-curing resin. Here, the isocyanate-curing resin contains a polyol compound and a polyisocyanate compound. When the resin contains an isocyanate-curing resin, the flexibility of the cured film of the adhesive can be moderately improved. In addition, the adhesion strength as a laminate can be further improved when a laminate obtained by applying the adhesive to the first substrate and laminating the second substrate is aged.
- The active energy ray-curable adhesive may further contain a leveling agent, an extender pigment, and the like as necessary.
- Examples of the resin in the active energy ray-curable adhesive include those exemplified as the resin as a raw material of the ink. Among them, an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, and a polyurethane resin are preferably used from the viewpoint of adhesion to the ink, film strength after curing, and the like.
- The resin in the active energy ray-curable adhesive preferably has an ethylenic double bond group, and inclusion of the resin having an ethylenic double bond group can further improve the strength of the cured film of the adhesive.
- The weight average molecular weight of the resin in the active energy ray-curable adhesive is preferably 20,000 or more and 50,000 or less. Here, the weight average molecular weight of the resin refers to a value in terms of polystyrene calculated using gel permeation chromatography (GPC).
- The content of the resin in the active energy ray-curable adhesive is preferably 10 mass% or more from the viewpoint of suppressing repelling of the adhesive at the time of application and further improving the flexibility of the cured film. On the other hand, the content of the resin in the active energy ray-curable adhesive is preferably 40 mass% or less from the viewpoint of suppressing back trapping by appropriately lowering the viscosity of the adhesive with respect to the ink and easily adjusting the viscosity (β1) described later to a preferable range described later.
- As the compound having an ethylenically unsaturated double bond, a monomer having an ethylenically unsaturated double bond is preferable. The compound having an ethylenically unsaturated double bond preferably have two or more ethylenically unsaturated double bonds in one molecule because it has high curability. On the other hand, the compound having an ethylenically unsaturated double bond preferably has six or less ethylenically unsaturated double bonds in one molecule from the viewpoint of improving the flexibility of the cured film of the adhesive. Among them, pentaerythritol tri(meth)acrylate, diglycerin tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, and ethoxylated trimethylolpropane tri(meth)acrylate are preferable.
- The content of the compound having an ethylenically unsaturated double bond in the active energy ray-curable adhesive is preferably 60 mass% or more from the viewpoint of improving the strength of the cured film of the adhesive and easily adjusting the viscosity β1 described later to a preferable range described later, and is preferably 90 mass% or less from the viewpoint of improving the flexibility of the cured film of the adhesive.
- The active energy ray-curable adhesive is preferably a non-solvent adhesive, that is, the content of the organic solvent is preferably 5 mass% or less, and the productivity can be further improved by eliminating the need for the drying step. The content of the organic solvent is more preferably 3 mass% or less.
- The viscosity β1 of the active energy ray-curable adhesive at a temperature of 30°C and a shear rate of 300s-1 is preferably 0.1 Pa · s or more and 20 Pa · s or less. The conditions of the temperature and the shear rate are assumed to be the temperature at the time of applying the adhesive and the shear rate when the adhesive is transferred onto the first substrate film and the ink having been transferred to the first substrate film. By setting the viscosity β1 to 0.1 Pa · s or more, adhesiveness of the adhesive to the second substrate after lamination and before the curing step can be improved. On the other hand, by setting the viscosity β1 to 20 Pa · s or less, the leveling property of the adhesive can be improved, and by setting the viscosity to be lower than that of the ink, back trapping can be suppressed. The viscosity β1 is more preferably 10 Pa · s or less.
- The ratio β1/α of the viscosity β1 of the active energy ray-curable adhesive to the viscosity α of the ink is preferably 0.01 or more and 1.0 or less. By setting the viscosity ratio β1/α to 0.01 or more, the adhesive can be applied to the uncured ink with good appearance. On the other hand, by setting the viscosity ratio β1/α to 1.0 or less, back trapping can be suppressed. By suppressing back trapping, the coating film of the adhesive can be uniformly formed, and adhesion as a laminate can also be improved.
- In order to set the viscosity ratio β1/α to the above range, the above-described resin and monomer having an ethylenically unsaturated double bond may be used for the ink and the adhesive. Further, the viscosity can be controlled by using a compound having all or any of the following characteristics as a monomer having an ethylenically unsaturated double bond that dissolves the resin used for the adhesive, and appropriately adjusting the proportion thereof.
- (1) The compound has hydrophilicity by ethoxylation. Thereby, the compatibility of the resin can be improved, and the viscosity can be moderately increased.
- (2) The compound has an alicyclic structure or a linear alkane structure. Thereby, the cohesive force of the adhesive resin solution can be suppressed, and the viscosity can be reduced.
- (3) The compound has a double bond equivalent of 100 or more. Thereby, the hydrogen bonding force by the acrylic group can be suppressed, and the viscosity of the adhesive can be suppressed.
- Here, the viscosity β1 of the active energy ray-curable adhesive in the present invention can be measured by the same method as in the above-described ink.
- The viscosity β1 of the active energy ray-curable adhesive can be adjusted to fall within the above-described range by, for example, using the above-described preferable resin and the compound having an ethylenically unsaturated double bond, and setting the molecular weight of the resin and the contents of the resin and the compound having an ethylenically unsaturated double bond to the above-described preferable ranges.
- The non-solvent isocyanate-curing adhesive preferably contains an isocyanate-curing resin and a compound having an ethylenically unsaturated double bond. When the non-solvent isocyanate-curing adhesive contains an isocyanate-curing resin, the adhesive can be applied to the uncured ink with good appearance. In addition, the flexibility of the cured film of the adhesive can be moderately improved. In addition, when the non-solvent isocyanate-curing adhesive contains a compound having an ethylenically unsaturated double bond, the viscosity of the non-solvent isocyanate-curing adhesive can be easily adjusted to a range suitable for processing, thus making it possible to improve the appearance of the laminated film. In addition, the adhesive can be cured by an active energy ray.
- The isocyanate-curing resin contains at least a polyol compound and a polyisocyanate compound.
- Examples of the polyol compound include polyether polyol, polyester polyol, and polycarbonate polyol. Two or more of these may be contained. Among them, polyether polyol and polyester polyol are preferable from the viewpoint of productivity. From the viewpoint of improving the leveling property of the coating film of the non-solvent isocyanate-curing adhesive, polyether polyol is more preferable, and from the viewpoint of improving the heat resistance in high temperature sterilization applications, polyester polyol is more preferable.
- Examples of the polyisocyanate include compounds having an aromatic isocyanate, an aliphatic isocyanate, an alicyclic isocyanate or the like at the terminal thereof. Two or more of these may be used. Among them, from the viewpoint of safety, a compound having an aliphatic isocyanate or an alicyclic isocyanate at the terminal thereof is preferable, and from the viewpoint of adjusting the reaction rate and viscosity, a compound having an aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic alicyclic diisocyanate at the terminal thereof is more preferable.
- Examples of the isocyanate-curing resin include a combination of a polyether polyol as a polyol compound and an aromatic polyisocyanate as a polyisocyanate, such as "TAKELAC" (registered trademark) A-244B/"TAKENATE" (registered trademark) A-244A, "TAKELAC" (registered trademark) A-246B/"TAKENATE" (registered trademark) A-246A, "TAKELAC" (registered trademark) A-248B/"TAKENATE" (registered trademark) A-246A manufactured by Mitsui Chemicals, Inc., and "EA-370A/EA-370B" manufactured by Toyo-Morton, Ltd.; and a combination of a polyester polyol as a polyol compound and an aliphatic, alicyclic, or aromatic alicyclic polyisocyanate as a polyisocyanate, such as "TAKELAC" (registered trademark) A-670B/"TAKENATE" (registered trademark) A-670A, "TAKELAC" (registered trademark) A-666/"TAKENATE" (registered trademark) A-65 manufactured by Mitsui Chemicals, Inc., and "TSN-4864A/TSN-4864B-3" manufactured by Toyo-Morton, Ltd.
- Examples of the compound having an ethylenically unsaturated double bond include monomers, oligomers, and resins having an ethylenically unsaturated double bond. Urethane (meth)acrylate is more preferable from the viewpoint of compatibility with the isocyanate-curing resin. As the urethane (meth)acrylate, those exemplified as the urethane (meth)acrylate in the ink are preferable.
- Examples of the resin having an ethylenically unsaturated double bond include an acrylic resin, a styrene acrylic resin, a styrene maleic acid resin, a rosin-modified maleic acid resin, a rosin-modified acrylic resin, and a polyurethane resin. Two or more of these may be contained. Among them, an acrylic resin, a styrene acrylic resin, and a styrene maleic acid resin are preferable from the viewpoint of ease of synthesis, adhesion to the ink, the strength of the coating film, and the like.
- The monomer having an ethylenically unsaturated double bond preferably has two or more ethylenically unsaturated double bonds in one molecule because it has high curability. On the other hand, the number of ethylenically unsaturated double bonds in one molecule is preferably 6 or less, and more preferably 4 or less from the viewpoint of improving the flexibility of the cured film of the adhesive and improving the adhesiveness of the adhesive to the second substrate before the lamination step. As such a monomer, those exemplified as the monomer having an ethylenically unsaturated double bond in the active energy ray-curable adhesive are preferable.
- The total content of the compound having an ethylenically unsaturated double bond in the non-solvent isocyanate-curing adhesive is preferably 1 mass% or more and 30 mass% or less. Here, the total content of the compound having an ethylenically unsaturated double bond refers to, when the adhesive contains only one of the monomer, oligomer, and resin having an ethylenically unsaturated double bond, the total content of the one of these, and when the adhesive contains two or more of these, the total contents of the two or more of these. By setting the total content thereof to 1 mass% or more, adhesion between the ink and the second substrate and the leveling property can be further improved. The total content thereof is more preferably 5 mass% or more. On the other hand, by setting the total content thereof to 30 mass% or less, adhesion between the ink and the second substrate after the isocyanate-curing component is cured by aging can be further improved.
- The non-solvent isocyanate-curing adhesive may further contain a leveling agent, an extender pigment, and the like as necessary.
- The viscosity β2 of the non-solvent isocyanate-curing adhesive at a temperature of 30°C and a shear rate of 300s-1 is preferably 1 Pa · s or more, and preferably 20 Pa · s or less. The viscosity β2' of the non-solvent isocyanate-curing adhesive at a temperature of 80°C and a shear rate of 300s-1 is preferably 0.05 Pa · s or more, and preferably 5 Pa · s or less. The conditions of the temperature and the shear rate are assumed to be the temperature range of 30 to 80°C at the time of applying the adhesive and the shear rate when the adhesive is transferred onto the first substrate film and the ink having been transferred to the first substrate film.
- By setting the viscosity β2 to 1 Pa · s or more, the adhesive can be applied to the uncured ink with good appearance, and the adhesiveness of the adhesive to the second substrate after the curing step and before the lamination step can be improved. The viscosity β2 is more preferably 5 Pa · s or more. On the other hand, by setting the viscosity β2 to 20 Pa · s or less, the leveling property can be improved. The viscosity β2 is more preferably 15 Pa · s or less.
- By setting the viscosity β2' to 0.05 Pa · s or more, the adhesive can be applied to the uncured ink with good appearance, and the adhesiveness of the adhesive to the second substrate after the curing step and before the lamination step can be improved. The viscosity β2' is more preferably 0.08 Pa · s or more. On the other hand, by setting the viscosity β2' to 5 Pa · s or less, the leveling property can be improved.
- The ratio β2/α of the viscosity β2 of the non-solvent isocyanate-curing adhesive to the viscosity α of the ink is preferably 0.01 or more and 0.50 or less. By setting the viscosity ratio β2/α to 0.01 or more, the adhesive can be applied to the uncured ink with good appearance. On the other hand, by setting the viscosity ratio β2/α to 0.50 or less, the occurrence of orange peel or the like can be suppressed in the application of the adhesive.
- In order to set the viscosity ratio β2/α within the above range, the above-described ink and the adhesive containing the above-described resin and compound having an ethylenically unsaturated double bond may be used. Further, the viscosity can be controlled by using a compound having all or any of the following characteristics as a monomer having an ethylenically unsaturated double bond, and appropriately adjusting the proportion thereof.
- (1) The compound has hydrophilicity by ethoxylation. Thereby, the compatibility of the resin can be improved, and the viscosity can be moderately increased.
- (2) The compound has a double bond equivalent of 100 or more. Thereby, the hydrogen bonding force by the acrylic group can be suppressed, and the viscosity of the adhesive can be suppressed.
- Here, the viscosities β2 and β2' of the active energy ray-curable adhesive in the present invention can be measured by the same method as the viscosity of the ink described above.
- The viscosities β2 and β2' of the non-solvent isocyanate-curing adhesive can be adjusted to fall within the above-described ranges by, for example, using the above-described preferable isocyanate-curing adhesive and the compound having an ethylenically unsaturated double bond, and setting the content of the compound having an ethylenically unsaturated double bond to the above-described preferable range.
- Next, each step of the first aspect and the second aspect will be described.
- The first aspect of the method for producing a laminated film of the present invention includes a printing step, an adhesive application step, a lamination step, and a curing step in this order.
- First, the printing step will be described. In the first aspect, the above-described ink is applied to the first substrate film. The printing method is preferably offset printing (lithographic printing) or flexographic printing that does not require the drying step and enables a plurality of times of laminations of uncured ink (wet-on-wet printing). Among them, offset printing is more preferable from the viewpoint of easily suppressing back trapping of the ink, and waterless offset printing is still more preferable from the viewpoint that contamination of the ink with a trace amount of moisture does not occur because the offset printing does not require a dampening solution, and radicals generated by irradiation with an active energy ray can be efficiently used for a curing reaction.
- Next, the adhesive application step will be described. In the first aspect, an active energy ray-curable adhesive is applied in-line to a printed material obtained by applying the ink to the first substrate by the above-described printing step. As a method for applying the adhesive, offset printing or flexographic printing is preferable because the adhesive is applied onto the uncured ink. Flexographic printing is more preferable because it is easy to increase the film thickness of the adhesive and it is suitable for applying a material having a relatively low viscosity. The application temperature of the adhesive is preferably 20°C to 40°C in order to maintain favorable viscosity and application appearance at the time of application.
- Examples of the printing press preferably used in the printing step and the adhesive application step include a center drum printing press "CI8" (manufactured by COMEXI). A coater having an existing active energy ray curing unit may be connected to the printing press.
- Next, the lamination step will be described. In the first aspect, the second substrate is bonded and laminated, with a nip roll, to the laminate obtained by sequentially applying the ink and the adhesive to the first substrate. The nip pressure is preferably 0.1 MPa or more and 0.6 MPa or less. The nip roll temperature is preferably 40°C or more and 80°C or less.
- Next, the curing step will be described. In the first aspect, the ink and the active energy ray-curable adhesive on the first substrate film can be quickly cured by irradiation with an active energy ray. The active energy ray used may be any ray as long as the ray has an excitation energy necessary for the curing reaction, and examples thereof preferably include electron beams and ultraviolet rays. When an electron beam is used, the ink can be cured without blending a photopolymerization initiator in the ink. Thus, the electron beam is particularly suitable for applications such as pharmaceutical packaging and food packaging in which migration of a low molecular weight compound to contents and odor peculiar to the initiator are avoided.
- When the active energy ray is applied from both sides of the first substrate and the second substrate, the curability of the ink and/or the adhesive can be improved, which is preferable. In particular, as in the first aspect, in the case of performing irradiation with an electron beam in a state where the first substrate and the second substrate are laminated, when electron beams are applied from both surfaces of the laminate, electron beams required for only curing the ink and/or the adhesive can be applied even by irradiation with electron beams at a low acceleration voltage. It is therefore possible to suppress deterioration of the substrate due to the electron beam.
- When the active energy ray is applied from only one of the first substrate film side and the second substrate side, it is preferable to apply the active energy ray from the side where the thickness is small or the side where the specific gravity of the substrate is small (when an aluminum foil is used for the second substrate, a side that is not an aluminum foil) from the viewpoint of more effectively proceeding the curing of the ink with the active energy ray. In addition, when a substrate having a relatively large change in physical properties due to the electron beam, such as a polypropylene film, is used, it is preferable to reduce the acceleration voltage contributing to the penetration depth of the electron beam and the irradiation dose contributing to the density of the electron beam within a range in which the ink and/or the adhesive is cured.
- When the curing is conducted by using an electron beam, an electron beam device emitting an energy ray of 100 to 500 keV is preferably used.
- The irradiation dose of the electron beam is preferably 10 kGy or more from the viewpoint of improving the curability of the ink and the active energy ray-curable adhesive. On the other hand, the irradiation dose of the electron beam is preferably 80 kGy or less from the viewpoint of suppressing deterioration and discoloration of the first substrate film and the second substrate.
- The acceleration voltage contributing to the penetration depth of the electron beam is preferably 80 kV or more and 300 kV or less. When the acceleration voltage is 80 kV or more, the electron beam can be stably generated. When the acceleration voltage is 300 kV or less, more preferably 150 kV or less, a change in physical properties of the substrate film can be suppressed.
- In the case of curing with ultraviolet rays, for example, an ultraviolet lamp such as a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or a light emitting diode (LED) is preferably used. A light emitting diode that emits a bright line having a wavelength of 350 to 420 nm is preferable from the viewpoint of power saving and cost reduction.
- In the curing step, the elastic modulus of the coating film of the active energy ray-curable adhesive after curing is preferably 5 MPa or more, and more preferably 10 MPa or more from the viewpoint of improving the flexibility and strength of the coating film. On the other hand, the elastic modulus of the coating film of the active energy ray-curable adhesive after curing is preferably 600 MPa or less, and more preferably 500 MPa or less from the viewpoint of suppressing generation of cracks and the like. The elastic modulus of the coating film is measured by a nanoindenter.
- Next, the second aspect of the present invention will be described. The second aspect of the method for producing a laminated film of the present invention includes a printing step, an adhesive application step, a curing step, and a lamination step in this order.
- The printing step and the lamination step are the same as those in the first aspect.
- In the adhesive application step, the non-solvent isocyanate-curing adhesive is applied in-line to the printed material obtained by applying the ink to the first substrate by the printing step without passing through the winding step. Examples of the method for applying the adhesive include the methods exemplified in the first aspect, and flexographic printing is preferable. The application temperature of the adhesive is preferably 20°C to 80°C in order to maintain favorable viscosity and application appearance at the time of application.
- Examples of the printing press preferably used in the printing step and the adhesive application step include those exemplified in the first aspect.
- Next, the curing step will be described. As in the first aspect, in the curing step, the ink on the first substrate film can be quickly cured by irradiation with an active energy ray. In addition, the initial adhesion strength can be improved by semi-curing the non-solvent isocyanate-curing adhesive to increase the apparent molecular weight thereof. In the second aspect, since the second substrate is not irradiated with an electron beam, a change in physical properties of the second substrate due to the electron beam can be prevented.
- The active energy ray used may be any ray as long as the ray has an excitation energy necessary for the curing reaction, and examples thereof preferably include electron beams and ultraviolet rays.
- The initial peel strength of the laminate obtained by the method for producing a laminated film of the present invention is preferably 0.5 N or more, more preferably 0.8 N or more, more preferably 1.0 N or more, still more preferably 1.5 N or more from the viewpoint of preventing appearance defects in post-processing.
- In particular, the peel strength after aging of the laminate obtained in the second aspect is preferably 1.5 N or more, more preferably 2.0 N or more, and still more preferably 3.0 N or more from the viewpoint of maintaining good strength as a packaging material. Here, the peeling strength of the laminate is measured in the section (8) of the evaluation method in Examples described later.
- Evaluation methods in the Examples and Comparative Examples are described below.
- The weight average molecular weight of the resin used in Examples and Comparative Examples is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase.
- Each resin was added to tetrahydrofuran so as to have a resin concentration of 0.25 mass%, and dissolved by stirring at a rotation speed of 100 rpm for 5 minutes using a shaker MIX-ROTAR VMR-5 (manufactured by AS ONE Corporation). The obtained solution was filtered with a 0.2 um filter Z227536-100EA (manufactured by SIGMA), and the filtrate was used as a measurement sample. Detection was performed using an RI detector built in a gel permeation chromatography apparatus HLC-8220 (manufactured by Tosoh Corporation). As a column, TSKgel SuperHM-H (manufactured by Tosoh Corporation), TSKgel SuperHM-H (manufactured by Tosoh Corporation), and TSKgel SuperH 2000 (manufactured by Tosoh Corporation) were connected in this order, the injection amount was 10 µL, the analysis time was 30 minutes, the flow rate was 0.4 mL/min, and the column temperature was 40°C. The weight average molecular weight of the resin was calculated from the calibration curve created using the polystyrene standard substance.
- The acid value of the resin was determined according to the neutralization titration in Section 3.1 of the test method of JIS K 0070: 1992.
- The iodine value of the resin was determined by the method described in Section 6.0 of the test method of JIS K 0070: 1992.
- The hydroxyl value of the monomer was measured according to the neutralization titration of Section 7.1 of the test method of JIS K 0070: 1992.
- The viscosity of the ink used in Examples and Comparative Examples was measured by the following procedure using a dynamic viscoelasticity measuring device Pyhsia MCR301 (manufactured by Anton Paar GmbH) using a cone plate jig having a cone plate with a diameter of 40 mm and an inclination angle of 1.00° and a lower plate, and having a gap between the cone plate and the lower plate of 81 µm. First, the dynamic viscoelasticity measuring device was heated to 30°C in advance, 0.7 mL of ink was placed between the heated cone plate and lower plate, and the cone plate jig is set at the measurement position and then allowed to stand at 30°C for 3 minutes. Next, the viscosity at a shear rate of 300s-1 was determined from an approximate curve of the shear rate and the viscosity obtained by measuring the viscosity of the ink while the shear rate is continuously changed logarithmically in the range of the shear rate of 1 to 490s-1 at a temperature of 30°C.
- The viscosities β1 and β2 of the active energy-curable adhesive and the non-solvent isocyanate-curing adhesive used in Examples and Comparative Examples were measured in the same manner as in the ink viscosity α described in the above section (5).
- The viscosity β2' of the non-solvent isocyanate-curing adhesive used in Examples and Comparative Examples was measured in the same manner as in the viscosities β1 and β2 except that the preheating temperature and the measurement temperature of the device were set to 80°C.
- A laminated film was produced in the same manner as in Examples and Comparative Examples except that a PET film "EMBLET" (registered trademark) PET 12 um (manufactured by UNITIKA Ltd.) was used instead of the film A as the first substrate. Since the ink in the obtained laminated film was subjected to a curing step under the same conditions as those in Examples and Comparative Examples, the curability of the ink in the laminated film obtained in Examples and Comparative Examples was evaluated from the ink in the laminated film obtained here.
- The obtained laminated film was allowed to stand at 40°C for 72 hours, that is, aged. Then, the PET film as the first substrate was peeled off, and the exposed surface of the ink cured product was rubbed with a cloth (No. 6 canvas) immersed in methyl ethyl ketone. The presence or absence of coloring of the cloth with the ink was visually observed. The curability of the ink was evaluated according to the following criteria from the number of reciprocations until the cloth was colored.
- A: 50 or more reciprocations
- B: 15 to 49 reciprocations
- C: 14 reciprocations or less.
- A section having a width of 15 mm and a length of 50 mm was cut out from the laminated film obtained in Examples and Comparative Examples. Under an environment of an air temperature of 25°C and a humidity of 50%RH, the first substrate film and the second substrate were respectively held with upper and lower chucks of a TENSILON universal material testing instrument RTG-1210 (manufactured by A & D Company, Limited), and a tensile test was performed at a test speed of 300 mm/min to measure a load value at a first maximum point. Measurement was performed three times, and the average value of the measurements was taken as the initial peel strength. Further, the section after the tensile test were visually observed, and the peeling mode was specified.
- The laminated film obtained in Examples and Comparative Examples was allowed to stand at a temperature of 40°C for 72 hours, that is, aged. Then, the peel strength after aging was measured by the same method, and the adhesion was evaluated. A case where the peel strength after aging was 2.0 N or more, or a case where the fracture mode was film breakage was evaluated as having good adhesion.
- The productivity was also evaluated from the initial peel strength and the peel strength after aging according to the following criteria.
- S: The initial peel strength and the peel strength after aging are both 1.5 N or more, and the difference between both peel strengths is 1.0 N or less
- A: The initial peel strength is 0.8 or more and less than 1.5 N, and the peel strength after aging is 1.5 N or more
- B: The initial peel strength is 0.5 N or more and less than 0.8 N
- C: The initial peel strength is less than 0.5 N.
- In Examples and Comparative Examples, the leveling property was visually observed from gloss and the presence or absence of ink voids in the solid part immediately after the ink was transferred to the first substrate film A, and the print appearance was evaluated according to the following criteria.
- S: The leveling property is particularly good
- A: The leveling property is good
- B: The leveling property is slightly poor.
- The laminated film obtained in Examples and Comparative Examples was visually observed, and the presence or absence of interlayer delamination, bubbles, and the like was observed.
- In Examples and Comparative Examples, the reflection density of the solid part after the printing step and before the adhesive application step and the reflection density of the solid part of the obtained laminated film were measured using a reflection densitometer ("SpectroEye" manufactured by GretagMacbeth LLC) in the measurement mode of status E, and the presence or absence of back trapping was evaluated from the difference between the reflection densities. In the measurement of the reflection density, a coated paper was used as a standard for the reflection density of 0.
- From these results, the laminate appearance was evaluated according to the following criteria.
- S: The color density change is less than 0.1, and interlayer delamination, bubbles, and the like are not observed
- A: The color density change is 0.1 or more and less than 0.3, and interlayer delamination, bubbles, and the like are hardly observed
- B: The color density change is 0.3 or more, or interlayer delamination, bubbles, or the like is observed.
- Materials used in Examples and Comparative Examples are shown below.
-
- First substrate film A: a polyester film having a urethane bond-containing easily adhesive layer and having a thickness of 12 um
- Second substrate film B: a cast polypropylene film having a thickness of 50 um, "TORAYFAN" (registered trademark) ZK207 (trade name) (manufactured by Toray Advanced Film Co., Ltd.).
- A resin having an ethylenically unsaturated double bond and a hydrophilic group (hydroxyl group and carboxyl group) was obtained by an addition reaction in which 0.55 equivalents of glycidyl methacrylate were combined with carboxyl groups of a copolymer of 25 mass% of methyl methacrylate, 25 mass% of styrene, and 50 mass% of methacrylic acid, and the obtained resin was used as a
resin 1. The obtainedresin 1 had a weight average molecular weight of 34,000, an acid value of 105 mgKOH/g, and an iodine value of 2.0 mol/kg. - A resin which was a copolymer of 25 mass% of methyl methacrylate, 25 mass% of styrene, and 50 mass% of methacrylic acid was used as a
resin 2. Theresin 2 has neither a hydrophilic group nor an ethylenically unsaturated double bond. The weight average molecular weight of theresin 2 was 30,000. - An oligomer having two ethylenically unsaturated double bonds at terminals thereof was used as a
urethane acrylate 1, and the oligomer was obtained from alicyclic diisocyanate (IPDI), polyether polyol (polytetramethylene ether glycol), and 2-hydroxyethyl acrylate. The weight average molecular weight of theurethane acrylate 1 was 3,300. - An oligomer having two ethylenically unsaturated double bonds at terminals thereof was used as a
urethane acrylate 2, and the oligomer was obtained from alicyclic diisocyanate (IPDI), polyether polyol (polytetramethylene ether glycol), and 2-hydroxyethyl acrylate. The weight average molecular weight of theurethane acrylate 2 was 13,000. - A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate "Miramer" (registered trademark) M340 (manufactured by MIWON) was used. The hydroxyl value of the
monomer 1 was 115 mgKOH/g. - Tricyclodecane dimethanol diacrylate "Miramer" (registered trademark) M262 (manufactured by MIWON) was used. The hydroxyl value of the
monomer 2 was 0 mgKOH/g. -
- Polymerization inhibitor: p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.)
- Pigment: Seika Cyanine Blue 4920 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)
- Extender pigment: "MICRO ACE" (registered trademark) P-8 (manufactured by Nippon Talc Co., Ltd.).
- The above ink raw materials were weighed in the following composition, and passed through a three roll mill "EXAKT" (registered trademark) M-80S (manufactured by Exakt Technologies.) five times with the setting "
Gap 1" in the apparatus to obtain a printing ink. - Resin 1: 11.7 mass%, monomer 1: 42.1 mass%, monomer 2: 25.1 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 3.0 mass%.
- Resin 1: 10.5 mass%, urethane acrylate 1: 10.0 mass%, monomer 1: 40.4 mass%, monomer 2: 20.0 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 1.0 mass%.
- Resin 1: 9.7 mass%, monomer 1: 43.1 mass%, monomer 2: 26.1 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 3.0 mass%.
- Resin 2: 18.0 mass%, monomer 1: 30.5 mass%, monomer 2: 30.4 mass%, polymerization inhibitor: 0.1 mass%, pigment: 18.0 mass%, extender pigment: 3.0 mass%.
- The
resin 1, themonomer 1, and themonomer 2 were blended in the compositions shown in Table 1, and the mixture was passed through a three roll mill "EXAKT" (registered trademark) M-80S (manufactured by Exakt Technologies.) five times with the setting "Gap 1" in the apparatus to obtain an active energy ray-curable adhesive. - Using an offset printing unit of a center drum printing press "CI8" (manufactured by COMEXI), the ink A was transferred onto the first substrate film A so that the application amount was 1.0 g/m2 to form an ink coating film (printing step). Using a flexographic printing unit of the center drum printing press "CI8" (manufactured by COMEXI), an adhesive A was applied onto the ink coating film so that the application amount was 2.0 g/m2 (adhesive application step), and the second substrate film B was laminated thereon using a nip roll (lamination step). Using an electron beam irradiation unit, the obtained laminate was irradiated with an electron beam from the first substrate film side under the conditions of an acceleration voltage of 110 kV and an irradiation dose of 30 kGy (curing step) to obtain a laminated film with the first substrate film A, the ink A, the active energy ray-curable adhesive, and the second substrate film B laminated in this order. The evaluation results of the obtained laminated film are shown in Table 1.
- Laminated films were produced in the same manner as in Example 1 except that the composition and ink of the active energy ray-curable adhesive were changed as shown in Table 1. The evaluation results of the obtained laminated films are shown in Table 1.
- A laminated film was produced in the same manner as in Example 1 except that the composition and ink of the active energy ray-curable adhesive were changed as shown in Table 1, and an electron beam was applied from both sides of the first substrate film side and the second substrate film side using an electron beam irradiation unit under the conditions of an acceleration voltage of 110 kV and an irradiation dose of 30 kGy. The evaluation results of the obtained laminated films are shown in Table 1.
- The ink A was transferred to the first substrate film A by the same method as in Example 1 (printing step), and electron beam irradiation was performed under the same conditions as in Example 1 (curing step) to obtain a laminate of the first substrate film A/cured film of the ink A.
- A mixture of a solvent-containing adhesive "TAKELAC" (registered trademark) A-969V/"TAKENATE" (registered trademark) A-5 manufactured by Mitsui Chemicals, Inc. at a mass ratio of 3/1 was applied onto the cured film of the ink A using a bar coater so that the application amount was 2.0 g/m2, and dried at 80°C for 1 minute (adhesive application step).
- Thereafter, the second substrate film B was laminated using a hand roller (lamination step) to obtain a laminated film with the first substrate film A, the ink A, the adhesive, and the second substrate film B laminated in this order. The evaluation results of the obtained laminated films are shown in Table 1.
[Table 1-1] Example 1 Example 2 Example 3 Example 4 Ink A B A D Adhesive for dry lamination - - - - Composition of active energy ray-curable adhesive [mass%] Resin 130 20 - 50 Resin 2 - - 50 - Monomer 135 40 25 25 Monomer 235 40 25 25 β1/α 0.32 0.11 0.72 0.53 Ink viscosity α [Pa·s] 25 35 25 45 Adhesive viscosity β1 [Pa·s] 8 4 18 24 Print appearance S A S B Laminate appearance S S A S Ink curability S S S S Initial peel strength [N] (Fracture mode) 2.4 (Film breakage) 2.6 (Film breakage) 1.8 (Film breakage) 1.7 (Film breakage) Peel strength after aging [N] (Fracture mode) 2.5 (Film breakage) 2.9 (Film breakage) 2.0 (Film breakage) 1.8 (Film breakage) Productivity S S S S [Table 1-2] Example 5 Example 6 Comparative Example 1 Ink C A A Adhesive for dry lamination - - 100 Composition of active energy ray-curable adhesive [mass%] Resin 150 30 - Resin 2 - - Monomer 125 35 - Monomer 225 35 - β1/α 3.00 0.32 <0.01 Ink viscosity ex [Pa -s] 8 25 25 Adhesive viscosity β1 [Pa·s] 24 8 0.02 Print appearance S S S Laminate appearance B S A Ink curability S S B Initial peel strength [N] (Fracture mode) 1.5 (Film breakage) 3.0 (Film breakage) 0.6 (Adhesive/second substrate) Peel strength after aging [N] (Fracture mode) 1.6 (Film breakage) 3.0 (Film breakage) 2.6 (Film breakage) Productivity S S B - Using an offset printing unit of a center drum printing press "CI8" (manufactured by COMEXI), the ink A was transferred onto the substrate film A so that the application amount was 1.0 g/m2 to form an ink coating film (printing step).
- Using a flexographic printing unit of the center drum printing press "CI8" (manufactured by COMEXI), a mixture of an isocyanate-curing adhesive "TAKELAC" (registered trademark) A-670B/"TAKENATE" (registered trademark) A-670A at a mass ratio of 5/10 was applied onto the ink coating film so that the application amount was 2.0 g/m2 (adhesive application step), and an electron beam was applied from the side of the surface to which the adhesive had been applied under the same conditions as in Example 1 (curing step) .
- Subsequently, the second substrate film B was laminated using a nip roll to obtain a laminated film. The evaluation results of the obtained laminate are shown in Table 2.
- "TAKELAC" (registered trademark) A-670 B/"TAKENATE" (registered trademark) A-670A" (mass ratio: 5/10) as isocyanate-curing resins, and the
resin 1 were blended in the compositions shown in Table 2 to obtain a non-solvent isocyanate-curing adhesive. Specifically, first, 30 parts by mass of "TAKELAC" (registered trademark) A-670B and 10 parts by mass of theresin 1 were mixed by passing these materials through a three roll mill "EXAKT" (registered trademark) M-80S (manufactured by Exakt Technologies.) five times with the setting "Gap 1" in the apparatus. Then, 60 parts by mass of "TAKENATE" (registered trademark) A-670A was added to 40 parts by mass of the obtained mixture, and the resulting mixture was manually shaken and stirred to prepare a non-solvent isocyanate-curing adhesive. - A laminated film was obtained in the same manner as in Example 7 except that the non-solvent isocyanate-curing adhesive was used. The evaluation results of the obtained laminated film are shown in Table 2.
- "TAKELAC" (registered trademark) A-670B/"TAKENATE" (registered trademark) A-670A (mass ratio: 5/10) as isocyanate-curing resins, and
urethane acrylate urethane acrylate - Laminated films were obtained in the same manner as in Example 7 except that the non-solvent isocyanate-curing adhesive was used. The evaluation results of the obtained laminated films are shown in Table 2.
- The ink A was transferred to the first substrate film A by the same method as in Example 1 (printing step), and electron beam irradiation was performed under the same conditions as in Example 1 (curing step) to obtain a laminate of the first substrate film A/cured film of the ink A.
- A mixture of a non-solvent isocyanate-curing adhesive "TAKELAC" (registered trademark) A-244B/"TAKENATE" (registered trademark) A-244A manufactured by Mitsui Chemicals, Inc. at a mass ratio of 5/10 was applied onto the cured film of the ink A using a bar coater so that the application amount was 2.0 g/m2 (adhesive application step).
- Thereafter, the second substrate film B was laminated using a hand roller (lamination step) to obtain a laminated film with the first substrate film A, the ink A, the adhesive, and the second substrate film B laminated in this order. The evaluation results of the obtained laminated films are shown in Table 2.
[Table 2] Example 7 Example 8 Example 9 Example 10 Comparative Example 2 Ink A A A A A Composition of non-solvent isocyanate curable adhesive [mass%] Isocyanate curable resin 100 90 90 90 100 Resin 1 - 10 - - - Urethane acrylate 1 - - 10 - - Urethane acrylate 2 - - - 10 - Monomer 1 - - - - - β2/α 0.32 0.48 0.36 0.44 0.32 Ink viscosity α [Pa·s] 25 25 25 25 25 Adhesive viscosity β2 [Pa·s] 8.0 12.0 9.0 11.1 8.0 Adhesive viscosity β2' [Pa·s] 0.5 4.5 2.2 3.1 0.5 Laminate appearance A S S S A Ink curability A S S S B Initial peel strength [N] (Fracture mode) 0.5 (Adhesive/secon d substrate) 0.8 (Adhesive/secon d substrate) 1.5 (Adhesive/secon d substrate) 1.0 (Adhesive/secon d substrate) 0.3 (Adhesive/second substrate) Peel strength after aging [N] (Fracture mode) 3.0 (Film breakage) 3.1 (Film breakage) 3.0 (Film breakage) 2.8 (Film breakage) 1.6 (First substrate/ink) Productivity B A S A C -
- 1: First substrate film
- 2: Offset printing unit
- 3: Flexographic printing unit
- 4: Nip roll
- 5: Second substrate
- 6: Electron beam irradiation device
Claims (15)
- A method for producing a laminated film, the method comprising:a printing step of applying an active energy ray-curable printing ink to a first substrate film formed of at least a plastic film;an adhesive application step of applying an adhesive; anda lamination step of laminating a second substrate,the steps being performed in this order in-line,the method further comprising a curing step of irradiating the active energy ray-curable printing ink with an active energy ray to cure the active energy ray-curable printing ink after at least the adhesive application step.
- The method for producing a laminated film according to claim 1, whereinthe adhesive is an active energy ray-curable adhesive,the method includes the curing step after the lamination step, andthe active energy ray-curable printing ink and the active energy ray-curable adhesive are cured in the curing step.
- The method for producing a laminated film according to claim 2, wherein a ratio β1/α of a viscosity β1 of the active energy ray-curable adhesive at a temperature of 30°C and a shear rate of 300s-1 to a viscosity α of the active energy ray-curable printing ink at a temperature of 30°C and a shear rate of 300s-1 is 0.01 or more and 1.0 or less.
- The method for producing a laminated film according to claim 2 or 3, wherein the viscosity β1 of the active energy ray-curable adhesive at a temperature of 30°C and a shear rate of 300s-1 is 0.1 Pa · s or more and 20 Pa · s or less.
- The method for producing a laminated film according to any one of claims 2 to 4, wherein the viscosity α of the active energy ray-curable printing ink at a temperature of 30°C and a shear rate of 300s-1 is 10 Pa · s or more and 40 Pa · s or less.
- The method for producing a laminated film according to any one of claims 2 to 5, wherein the active energy ray-curable adhesive contains at least a resin and a compound having an ethylenically unsaturated double bond.
- The method for producing a laminated film according to claim 1, whereinthe adhesive in the adhesive application step is a non-solvent isocyanate-curing adhesive, andthe method includes the curing step before the lamination step.
- The method for producing a laminated film according to claim 7, wherein a ratio β2/α of a viscosity β2 of the non-solvent isocyanate-curing adhesive at 30°C and a shear rate of 300s-1 to a viscosity α of the active energy ray-curable printing ink at 30°C and a shear rate of 300s-1 is 0.01 or more and 0.50 or less.
- The method for producing a laminated film according to claim 7 or 8, wherein the viscosity β2 of the non-solvent isocyanate-curing adhesive at a temperature of 30°C and a shear rate of 300s-1 is 1 Pa · s or more and 20 Pa - s or less, and a viscosity β2' at a temperature of 80°C and a shear rate of 300s-1 is 0.05 Pa · s or more and 5 Pa · s or less.
- The method for producing a laminated film according to any one of claims 7 to 9, wherein the viscosity α of the active energy ray-curable printing ink at a temperature of 30°C and a shear rate of 300s-1 is 10 Pa · s or more and 40 Pa · s or less.
- The method for producing a laminated film according to any one of claims 7 to 10, whereinthe non-solvent isocyanate-curing adhesive contains an isocyanate-curing resin and a compound having an ethylenically unsaturated double bond, anda total content of the compound having an ethylenically unsaturated double bond is 1 mass% or more and 30 mass% or less.
- The method for producing a laminated film according to any one of claims 1 to 11, wherein the active energy ray-curable printing ink contains a resin and a compound having an ethylenically unsaturated double bond.
- The method for producing a laminated film according to any one of claims 1 to 12, wherein the compound having an ethylenically unsaturated double bond contains a urethane (meth)acrylate.
- The method for producing a laminated film according to claim 13, wherein a weight average molecular weight Mw of the urethane (meth)acrylate is 500 to 10,000.
- The method for producing a laminated film according to any one of claims 1 to 14, wherein the active energy ray in the curing step is an electron beam.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021054814 | 2021-03-29 | ||
PCT/JP2022/014330 WO2022210340A1 (en) | 2021-03-29 | 2022-03-25 | Method for producing film laminate |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4316838A1 true EP4316838A1 (en) | 2024-02-07 |
Family
ID=83458912
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP22780553.8A Pending EP4316838A1 (en) | 2021-03-29 | 2022-03-25 | Method for producing film laminate |
Country Status (5)
Country | Link |
---|---|
US (1) | US20240166916A1 (en) |
EP (1) | EP4316838A1 (en) |
JP (1) | JPWO2022210340A1 (en) |
CN (1) | CN117098664A (en) |
WO (1) | WO2022210340A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7326673B1 (en) * | 2023-02-22 | 2023-08-16 | サカタインクス株式会社 | Laminate containing primer layer |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4489497B2 (en) | 2004-05-20 | 2010-06-23 | 大日本印刷株式会社 | Laminated body with indicator for heat treatment and method for producing the same |
JP2010209274A (en) * | 2009-03-12 | 2010-09-24 | Riso Kagaku Corp | Active energy ray curable ink |
JP2011026551A (en) * | 2009-05-21 | 2011-02-10 | Kaneka Corp | Ultraviolet-curing type pressure-sensitive adhesive composition |
JP5578060B2 (en) * | 2010-01-15 | 2014-08-27 | 東洋インキScホールディングス株式会社 | Active energy ray curable adhesive |
JP6431673B2 (en) * | 2014-01-24 | 2018-11-28 | 武内プレス工業株式会社 | Method for manufacturing raw material for tube container and tube container made from this raw material |
JP6664846B2 (en) | 2016-08-19 | 2020-03-13 | 東洋インキScホールディングス株式会社 | Laminate and manufacturing method thereof |
WO2018117079A1 (en) * | 2016-12-21 | 2018-06-28 | Dicグラフィックス株式会社 | Active energy ray-curable printing ink composition, and printing method using same |
WO2020235557A1 (en) | 2019-05-22 | 2020-11-26 | 東レ株式会社 | Printing ink, method for producing printed work using said ink, and printed work |
-
2022
- 2022-03-25 WO PCT/JP2022/014330 patent/WO2022210340A1/en active Application Filing
- 2022-03-25 JP JP2022520731A patent/JPWO2022210340A1/ja active Pending
- 2022-03-25 EP EP22780553.8A patent/EP4316838A1/en active Pending
- 2022-03-25 US US18/283,297 patent/US20240166916A1/en active Pending
- 2022-03-25 CN CN202280024647.0A patent/CN117098664A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20240166916A1 (en) | 2024-05-23 |
WO2022210340A1 (en) | 2022-10-06 |
JPWO2022210340A1 (en) | 2022-10-06 |
CN117098664A (en) | 2023-11-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7237199B2 (en) | Low migration electron beam curing primer | |
JP6888619B2 (en) | Printed matter manufacturing method and printing machine | |
EP4316838A1 (en) | Method for producing film laminate | |
WO2020235557A1 (en) | Printing ink, method for producing printed work using said ink, and printed work | |
JP2013203069A (en) | Printing sheet and method of manufacturing the same | |
JPH08218295A (en) | High gloss sheet | |
JP7416060B2 (en) | Coating agent for printing film, laminate, and method for producing printed matter | |
EP4198097B1 (en) | Image forming method and active energy ray-curable composition set | |
EP3950368A1 (en) | Method for manufacturing printed matter | |
JP7371809B2 (en) | Electron beam curing overcoat varnish and food packaging materials | |
EP3700975B1 (en) | Actinically curable adhesive composition with improved properties | |
WO2020235556A1 (en) | Actinic-ray-curable lithographic printing ink and method for producing print using same | |
EP4189022B1 (en) | Low migration eb curable inks with bio-renewable content | |
JP7392225B2 (en) | Electron beam curable composition, food packaging material and manufacturing method thereof | |
EP4025424B1 (en) | Water-based barrier adhesive | |
JP5782717B2 (en) | Ink jet recording medium and method of manufacturing ink jet recording medium | |
WO2023013571A1 (en) | Printed matter manufacturing method, printing ink set, and printed matter | |
JP2002309021A (en) | Highly glossy film | |
CN117999297A (en) | Resin, active energy ray-curable composition, active energy ray-curable ink, overcoating varnish, paint, adhesive, photoresist, and method for producing printed matter | |
JP2024031605A (en) | Electron beam curable composition and food packaging material | |
JPH09250097A (en) | Basal paper for metallization | |
JP2002361802A (en) | Electron beam curable process release sheet | |
JP2023049235A (en) | Coating agent for printing film, laminate, and method for manufacturing printed matter | |
TW202336047A (en) | Active energy ray-curable compositions, ink compositions, ink compositions for two or three-dimensional molding, adhesive compositions, bonding compositions, paint compositions, sealant compositions, nail cosmetic, decorative coating agent, and dental materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20230927 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) |